Inorganic Chemistry Course Chapter 1: Elements, Compounds, Atoms and Electron Orbitals

Course on Inorganic Chemistry
by Frank Klose
Chapter 1
Elements and Compounds,

Atoms and Molecules
Structures and Bonds
Substances, Compounds and Elements
Substances
Heterogeneous Homogeneous
substances substances
Solutions Pure substances
Compounds Elements
The Discovery of the Chemical Elements
Antiquity/Middle Ages - The Four Elements

Fire, Water, Earth, and Air
1642 Jungius - Pioneer works on the present-day theory of

1661 R. Boyles chemical elements, definition of the terms
1777 Lavoisier element and compound (Lavoisier)
1869 - Proposal of the Periodic Table of Elements by

Mendelejew and Meyer (independently)
1999 - Discovery of the elements 114
(Joint Institute for Nuclear Research Dubna,
Russia), 116, 118 (Berkeley, California, USA)
Number of elements discovered
200 175
150
115
100 82
50 32
12 14 15
0
Antiquity 19th century

13th century 20th century
17th century Theoretical maximum
18th century
Percentage of Elements
Earths crust Human biomass

Element Percentage Percentage Element
[mg/kg] [mg/kg]
O 467600 O* 611000
Si 278600 C* 236000
Al 81600 H* 94000
Fe 50200 N* 28000
Ca 36400 Ca* 14000
Na 28400 P* 9330
K 26000 S* 2330
Mg 21000 K* 2270
Cl 18100 Na* 1400
Ti 4400 Cl* 1400
H 1400 Mg* 440
P 1000 Fe * 56
Mn 950 Zn* 40
F 625 Si* 18.7
Ba 425 Rb 18.7
Sr 375 F* 10.7
S 260 Sr 4
C 200 Zr 4
N 20 Cu* 2.67
Zr 165 Br 1.87
V 135 Sn* 1.87
Cr 100 Nb 1.33
I* 0.933
Rb, Ni, Zn, Ce, Cu, Y, 10 - 100 Al 0.467
La, Nd, Co, Sc, Li, Nb, Pb 0.467
Ga, Pb, Th, B Cd 0.4
Ba 0.267
Mn* 0.267
Pr, Br, Sm, Gd, Ar, Yb, 1 - 10 V* 0.267
Cs, Dy, Hf, Er, Be, Xe, B 0.187
Ta, Sn, U, As, W, Mo, Se * 0.187
Ge, Ho, Eu
Mo* 0.0667
As* 0.0467
Tb, I, Tl, Tm, Lu, Sb, 0.1 1 Co* 0.0373
Cd, Bi, In Cr* 0.0267
Li 0.0267
Hg, Ag, Se, Ru, Te, Pd, < 0.1 Ni* 0.0133
Pt, Rh, Os, Ne, He, Au,
Re, Ir, Kr, Ra, Pa, Ac, *) essentially
Po, Rn, Np, Pu, Pm, Fr,
At, Transplutonium
elements
The Atom and its Components
1808 - Hypothesis of atoms by Dalton

1897 - Discovery of the electron by J. J. Thomson
1913 - Discovery of the proton by E. Rutherford
1911 - Electron scattering experiments by
E. Rutherford Atom model concept proposing
a dense positive charged core and a negative
charged but near mass less shell filled with
electrons
1921 - Discovery of the neutron by W. D. Harkins
1926 - Schrdinger equation, begin of the quantum
mechanical description of atoms
1932 - Atom model by W. Heisenberg using electron
orbitals
Atom
Core Shell
Protons Neutrons Electrons
positive no negative
charged charge charged
contain the mass responsible for chemical

of an atom properties (outer e-)
Core/shell ratios :
- 10-4 with respect to the radius
- 5000 : 1 with respect to the mass
(99.95 99.98 % of the atom mass is concentrated in the core)
Atomic Constants and Dimensions
Masses
absolute mass of a proton: 1.6726 * 10-27 kg
absolute mass of a neutron: 1.6749 * 10-27 kg
absolute mass of an electron: 9.1093 * 10-31 kg
absolute mass unit u [amu] = 1/12 * m(12C)

= 1.6605 * 10-27 kg
Relative masses of atoms (Ar) and molecules (Mr)
Ar or Mr = (mA or mM)/u (IUPAC 1961)
Molar masses M [g/mol]

M = m * NA
Numbers of Ar or Mr and M are identically!
Radius of atoms: 0.33 * 10-10 m

(10-10 m = 1 (Angstroem))
Other important constants

e - elementary charge: 1.6022 * 10-19 C
NA - Avogadro number: 6.0221 * 1023
h - Planck constant: 6.6261 * 10-34 J * K-1
Fundamental Equations from Quantum Mechanics
Schrdinger equation (1926)
H = E
H Hamilton operator
E Energy of the electron
- Wave functio n
The Uncertainty Principle by Heisenberg (1927)
x * p h/4
x uncertainty of the position of the electron
p - uncertainty of the impulse of the electron
h Planck constant
Electron orbitals as the solutions of the Schrdinger equation:
rooms of highest probability (90 % or more) of finding the electron

motion of electrons in the orbitals is free of energy loss
electron energy levels are discrete
Electron Orbitals of Atoms
s orbital px orbital py orbital pz orbital
dxy orbital dxz orbital dvz orbital
d x 2 y 2 orbital d z 2 orbital
Algebraic signs are related to the angular part of the wave function, not to a charge!
Quantum Numbers for Electron Orbitals
The three fundamental properties of electrons: mass, charge, spin
The Pauli principle (Wolfgang Pauli, 1924):

No more than two electrons can occupy any given orbital. If two electrons
do occupy one orbital, then their spins must be paired.
Every electron orbital can be characterised by a set of quantum numbers

definitely.
n principal number
- determines the number of the shell (n = 1, 2, 3, )
- sometimes shells named with capital letters K, L, M,
(e.g. X-ray analysis)
l orbital angular momentum quantum number (subshell number)

- determines the type of electron orbital (s, p, d, f, g, )
- l can range from 0 to (n - 1)
- number of orbitals of a shell n is n
m orbital magnetic quantum number

- determines the orientation of the orbital (x, y, z, )
- unoccupied orbitals differing in m have the same energy
(they are degenerated)
- energy split in many electron systems (coupling of angular and
magnetic momentum, Coulomb interactions)
- m = 0, 1, 2,, l,
s spin magnetic quantum number

- the only values: - , +
additionally:
j angular momentum quantum number
- j = l s, (all possible combinations of l and s)
The Energy Scheme for Electron Orbitals
Energy 7d
7p
n=7
7s
Building up principals:
- Electrons occupy shells and orbitals in order of their energies (defined
by n and l).
- Each inner shell should be fully filled before occupying the next shell.
- Fully occupied subshells (s 2, p6, d 10, f14) have the highest stability. Half
occupied d subshells (d 5) are favoured, too.
- Hunds rule: An atom in its ground state adopts a configuration with
the greatest number of unpaired electrons. Electrons occupy different
orbitals of a given subshell before doubly occupying any one of them
(s is maximised).
- Outer electron configuration (valence electrons) determines chemical
properties.
- RESULT: Periodicity of number of valence electrons

by sequential filling of s, p, d and f orbitals
Periodicity - The Size of Atom Orbitals
electron
core
2nd shell
1st shell
electron
core
3rd shell
2nd shell
1st shell
Radius of orbitals of neutral atoms
contraction with increased proton number for each shell

(increased Coloumb attraction between the positive charged core and the
negative charged electron shell)
Positive ions are smaller and negative ions are larger compared to the
neutral atom.
Energy of orbitals is specific for each element.
Periodicity Ionisation Energies
First and second ionisation potential
Electron affinity
Atomic Spectroscopy
Principle of spectroscopy
Excitation Relaxation,
(specific or non-specific), Emission
absorption of specific radiation
Atom Absorption Spectroscopy (AAS)/ Term scheme for sodium (Na)

Optical Emission Spectroscopy
(OES, OES-ICP)
using of outer electron transitions

(l = 1, j = 0, 1,
s p and p d transitions)
specific for each element
laser technology
X-ray Flourescence Spectrometry (XFS)
using of inner electron transitions

(l = 1, j = 0, 1, s p and p d transitions)
XFS: primary relaxation, applicable for elements with Z = 9 - 92
(1) absorption of primary X-ray

radiatation
primary remove of a inner
X-ray radiatation electron ionisation
(2) transfer of an electron from
an outer shell to the leak
(3) emission of secondary X-ray
secondary radiation (specific for the
X-ray element)
radiatation
electron energy [eV]

The Periodic Table of Elements (PTE)
Main group elements

Ia IIa IIIa IVa Va VIa VIIa VIIIa
d block elements
n
(transition metals)
IIIb IVb Vb VIb VIIb VIIIb Ib IIb
Lanthanides
Actinides
s block d block p block

(l = 0) (l = 2) (l = 1)
Ia VIIIa, Ib VIIIb = group numbers

1-7 = numbers of periods
atomic number Z
(= number of protons)
rel. atomic mass
(= molecular mass)
electron
negativity
chemical symbol
name of the element colour = metallic or non-metallic character or

acid-base properties of the oxides
Prediction and Discovery of Germanium
1869- Mendelejew Proposal of the Periodic Table of Elements,

1871 Prediction of properties of the undiscovered element
32 based on the periodicity concept Table of
Elements
1886 Winkler Discovery of Germanium in a silver containing

mineral
Properties Properties found Present State

Proposed by by Winkler
Mendelejew 1886
1871
relative atom mass 72 72.32 72.61

colour dark grey grey white grey white
density [g/cm] 5.5 5.47 5.32
specific heat capacity [J/gK] 0.306 0.318 0.310
melting point [C] high - 937.4
valency 4 4 4
oxide formula AO2 GeO 2 GeO 2
density [g/cm] 4.7 4.703 4.228
acid/base predominantly acknowledged acknowledged
properties acid
chloride formula ACl4 GeCl4 GeCl4
density [g/cm] 1.9 1.887 1.8443
boiling point [C] 60 - 100 86 83.1
ethyl compound formula A(C 2 H5 )4 Ge(C 2 H5 )4 Ge(C 2 H5 )4
density [g/cm] 0.96 0.99 0.991
boiling point [C] 160 163 162.5
Historical Development
of Understanding Chemical Bonds
1789 Lavoisier Theory of radicals
1807 Davy Chemical bonds as electrochemical attraction,

1812 Berzelius Discrimination between electropositve and
electronegative elements
1852 Frankland Definition of valence as the ability of a given atom to

form a compound with a defined number of other atoms
(valency)
1857/58 Kekul Multiple carbon bonds in organic substances,

Kolbe first cyclic structure of benzene
Couper
1861 Butlerov Theory of chemical structures,

determined by valence bonds
1874 vant Hoff Stereochemistry

Le Bel
1910 Stark Coherence between valency and outer electrons

Falk (term valence electrons)
Nelson
1916-19 Lewis Octet rule (noble gas shells),

Langmuir ionic and covalent bonds,
Kossel covalent bonds as shared electron pairs
1927-29 Hund Mulliken Quantum mechanical LCAO-MO-theory

Lennard-Jones
1927-31 Heitler, Quantum mechanical valence bond theory

London, Slater,
Pauling
1931 Pauling Hybridisation

Types of Chemical Bonds (1)
Octet rule:
The electron configuration of noble gases (s 2, s 2p6, s 2p6d10,
s 2p6d10f14 fully saturated shells) have the highest stability. Every atom
tries to reach the electron configuration of the next neighboured noble gas
by donating or accepting electrons.
(8 valence electrons for elements of the 2nd and 3rd period)
Please note: At the higher periods also other electron configurations, like
(n-1)d10, (n-1)d10 (n)s 2, ((n-1)d5(n)s 2 can be preferred.
Covalent bonds
- sharing of electron pairs (electrons have different spins) between the
bonded atoms
- If the partners are equal, the electron pair belongs to both partners in
equal proportions, no dipole momentum can be observed.
- If the partners are different, the electron pair shifts to the atom with the
stronger electron affinity (electron negativity).
The bond will be polarised.
- dominates if difference of electron negativity is less than 1.7
- Valence Shell Electron Pair Repulsion Model (VSEPR):
Isolated electron pairs cause angled molecules (e.g. H2O).
CH4 NH3 H2O
109.5 107 104.9

Ionic bonds
- Move of electrons from one partner to the another,
ions electrically charged arise
- Bond is based on electric attraction of opposite ion charges.
- dominates if difference of electron negativity is higher than 1.7
atomic bond polarised covalent bond ionic bond
polarity of the ions
polarisation of the covalent bond
There exists a continuum between covalent and ionic parts of bonds!
Molecule Ionic part of the Molecule Ionic part of the

bond bond
LiF 0.87 NO 0.015
LiCl 0.73 CO 0.01
LiBr 0.59 HCl 0.18
LiI 0.55 HBr 0.12
CsCl 0.75 HI 0.05
BaO 0.43 H2 0
Metallic bonds
- atom cores form a crystal lattice, valence electrons and orbitals are
delocalised over the whole crystal (electron gas)
- exits only in solid or liquid metals
- The energy difference between the highest occupied molecule orbital
(HOMO) and the lowest un-occupied molecule orbital (LUMO) is
responsible for electrical conductivity:
- low in case of metals (easy and fast electron transition),
- moderate in case of semiconductor metals
- high in case of isolators
Intermolecular interactions
- van der Waals attraction
(weak interactions between the molecules, in general)
- Hydrogen bridging bonds
between acid H atoms and O, N or F atoms (2nd period)
intermolecular or intramolecular
Formic acid (intermolecular Maleic acid

H bridging bounds) (intramolecular
H bridging bounds)
Valency and Oxidation State Numbers
describe the number of electrons

which one atom spends or attracts in a molecule
is the charge of an atom/ion, which would occur,
if the reaction considered is described as a heterolytic reaction forming
ions
Oxidation states:
- are 0 for the elements in general
(also in molecules Ax, e.g. H2, O2, P 4, S8)
- are negative if a atom attracts electrons
(corresponding to charge)
e.g. O2-: -2, F-: -1
- are positive if a atom spends electrons
e.g. Na+: +1, Fe3+ : +3
- within a molecule the sum of oxidation states must be 0
(condition of electroneutrality)
- within an ion the sum of oxidation states
must give the overall charge of the ion
e.g. SO42-: S +6, O -2; 1 (+6) + 4 (-2) = -2
- within a chemical equation the sum of oxidation states
must be equal on both sides
e.g: 2 SO2 + O 2 2 SO3
left side: 2 (+4) + 4 (-2) + 2 (0)= 0
right side: 2 (+6) + 6 (-2) = 0
Mg + 2 H+ Mg2+ + H2
left side: 1 (0) + 2 (+1) = 2
right side: 1 (+2) + 2 (0) = 0
Valency state numbers:

- are the absolute (positive values) of oxidation state numbers
e.g. Na+: I, O2-: II
- are written in Roman numerals
Quantum Mechanical Concepts of Molecular Bonds
1. Theory of Molecular Orbitals (MO Theory)
Forming a molecule the atoms have to overlap their atom orbitals.
Linear combination of atom orbitals to molecular orbitals

(LCAO-MO theory) by Hund, Mulliken, Lennard-Jones (1927-1929)
positive interference negative interference no interference
Algebraic signs are related to the angular part of the wave function, not to a charge!
- interference can occur, if the atom orbitals have the same symmetric
properties with respect to the bond axis
- number of MO is equal to the number of interacting atom orbitals
- positive interference: bonded MO, decrease of energy
- negative interference: anti-bonded MO, increase of orbital energy
orbital orbital orbital
- number of bonds =
number of bonded MO - number of anti-bonded MO
2. Theory of Valence Bonds (VB Theory)
Heitler, London, Slater, Pauling (1927-1931)
Coupling of unpaired electrons to bonds gives molecular valence structures.
H + H H-H H? H? H? H?
The coupled electron pair can belong to

- both partners: covalent electron pair
- one atom: ionic electron pair
Favoured valence structure:

- maximized number of covalent bonds
- structures with short bond lengths
- ionic structures, where the electron pair is situated at the atom with
highest electron affinity
- ionic structures, where opposite charges are situated in the next
neighbourhood
The overall wave function is represented by the linear combination of all

possible valence structures.
Each valence structure can be transformed easily to another valence structure

(resonance). Valence structures are mesomeric borderline cases of the reality.
3. Hybridisation
Linus Pauling (1931)
Linear combination of s, p (and d) orbitals forms new hybrid orbitals.

Combination of LCAO-MO method and VB theory
Overlaying the atom orbitals Resulting hybrid orbitals
Type of Involved Geometric Type of the Geometry of Example

hybrid atom orbitals form molecule the molecule
orbital
sp s, px linear AB2 linear BeCl2
sp s, px , py triangle AB3 triangle BF3
AB2 V form SO2
sp s, px , py , pz tetrahedral AB4 tetrahedral CH4
AB3 triangle NH3
pyramid
AB2 V form H2 O
spd s, px , py , dxy quadratic AB4 quadratic XeF4
spd s, px , py , pz, triangle AB5 triangle PF5
dz2 bipyramidal bipyramidal
(2 tetra- AB3 T form ClF 3
hydrons) AB2 linear XeF2
spd s, px , py , pz, quadratic AB5 quadratic BrF5
dx 2 y 2 pyramid pyramid
spd s, px , py , pz, octahedron AB6 octahedron SF6
dz2 , dx 2 y 2 AB5 quadratic BrF5
pyramid
AB4 quadratic XeF4
Special Cases of Hybrid Orbitals
Ethylene Acetylene
(C-C double bonds) (C-C triple bonds)
= bond + bond = bond + 2 bonds

(sp2 hybrid orbitals) (sp hybrid orbitals)
Diborane B2H6 Benzene

(electron shortage compounds) (aromatic systems)
2 electrons triple center bond delocalised conjugated system
Multiple bonds occur only with elements of the 2nd period. At higher periods
they will be prevented by polymerisation (e.g. CO2 vs. SiO 2).
Literature/References for Figures
(1) Arnold Frederik Holleman, Egon Wiberg,

Lehrbuch der anorganischen Chemie
101st edition, Berlin [u.a.] : de Gruyter, 1995
A lot of pages (2033), and a lot of detailed information, the standard book for
inorganic chemistry in Germany
(2) Gisbert Gromann, Jr gen Fabian,

Lehrwerk Chemie, Lehrbuch 1 Struktur und Bindung Atome und Molekle,
6th edition, VEB Deutscher Verlag fr Grundstoffindustrie, 1989
The first book from a series, related to all topics of chemistry studies. Small and
compact (252 pages). It was used as the standard book in the former GDR.
(3) P.W. Atkins,

Physical Chemistry,
6th edition, Oxford University Press, 1998
A well readable book on basic level about all topics on physical chemistry.
(4) Richard Stephen Berry, Stuart A. Rice, John Ross,

Physical chemistry,
2nd edition, Oxford Univ. Press, 2000
Trends in the Periodic Table of Elements
ability to be oxidised
electron affinity/negativity, ionisation energy

metallic character
non-metallic character
basic strenght of oxides
acid strenght of oxides
Ia IIa IIIa IVa Va VIa VIIa VIIIa
IIIb IVb Vb VIb VIIb VIIIb Ib IIb
electron affinity,
Lanthanides
ionisation energy,
non-metallic character,
acid strenght of oxides, Actinides
oxidation state (valency)
Chapter 2
Chemical Reactions
The Chemical Equilibrium
Consider the reaction

A + B
k
C + D with r1 = k1 * [A] * [B]
1
If back reaction

C + D
A + B with r-1 = k-1 * [C] * [D]
k 1
also occurs, we have a chemical equilibrium described by
k1 [C ] [ D]
K= =
k 1 [ A ] [ B ]
Mass Action Law
(K equilibrium constant, k1 and k-1 rate constants for the reactions,
[A], [B], [C], [D] concentrations or partial pressures, , , , reaction orders )
Transition state theory (Eyring)
activated complex k1 = k0, 1 * exp (-EA, 1/RT)

energy
catalyst k-1 = k0, -1 * exp (-EA, -1 /RT)
EA, 1 EA, -1
In case of equilibrium
A+B r1 = r-1 0
C+D
dynamic equilibrium
reaction coordinate
Special cases:
cA , phase1
(1) Nernsts distribution law K=
cA , phase2
K cA , liqiuid solution
(2) Henry Daltons law K = =
RT p A , gas phase
[ B] + [ A]
(3) electrolytic dissociation Kc =
[ AB]
(K c < 10 - weak electrolytes, Kc > 10-4 - intermediate electrolytes,
-4
Kc 8 - strong electrolytes (full dissociation))

Le Chateliers Principle (1888)
A system in equilibrium, when subjected to a disturbance, responds in a way that

trends to minimise the effect of disturbance.
(1) Increase of temperature

favours the endothermic reaction
Decrease of temperature
favours the exothermic reaction
(2) Increase of pressure

favours the reaction with rV < 0
Decrease of pressure
favours the reaction with rV > 0
(3) Increase of the concentration of one reactant

favours the reaction consuming this reactant
Removal of one reactant
favours the reaction of its re-formation
Note: Catalysts increase both reaction rates r1 and r-1, so that the equilibrium is
reached faster, but under identical reaction conditions the distribution between the
reactants doesnt change.
Reduction and Oxidation
Oxidation
Reducing Oxidising
Reduction + electrons
agent agent
Oxidation number/oxidation degree:

charge of an atom, which would occur, if the reaction considered is described
as a heterolytic reaction forming ions
Examples: elements 0
HCl Oxidation number of hydrogen +1
Oxidation number of chlorine 1
H2O Oxidation number of hydrogen +1
Oxidation number of oxygen 2
The negative charge must attributed to the partner with the highest electron
negativity (see Periodic Table of Elements!!).
Electrochemical Potentials
electrical connection
Zn pole Cu pole
ZnSO4 solution CuSO4 solution
membrane
Galvanic cell (voluntary)

Anode (negative pole - oxidation):
Zn Zn2+ + 2 e-
Cathode (positive pole - reduction):
Cu2+ + 2 e- Cu
The back reaction is electrolysis forced by applying the opposite voltage.

Electrochemical Potential Series
- Potentials are relative values.

Normalisation on H2/2 H+ standard electrode (= 0.000 V)
- Nomenclature: reduced/oxidised species (Na/Na+, 2 Cl-/Cl2)
- low potential (negative e.g. alkali metals)
= high reduction power = easy to be oxidised
- high potential (positive e.g. noble metal cations)
= high oxidation power = easy to be reduced
allow to predict reactions (G = Z*F*)

applied in practice in electrochemical processes (e.g. galvanisation), in batteries
and fuel cells
Concentration dependency of potentials
R T c
Nernst Equation: = 0 + lg Ox .
Z F c Re d .
potential
0 standard potential (see tables)
R gas constant
T temperature
Z number of electrons, which should be donated or accepted
F Faraday constant
cOx./cRed. concentration of oxidised/reduced reactants (like in the mass action law)
Setting to 0, it is possible to get the equilibrium constant K.

Normalised potentials for acid (pH = 0) and
basic (pH = 14) solutions (at 25 C)
a) metals
acid solution basic solution
b) non-metallic elements and compounds

acid solution basic solution
Power of oxidising agents which are reduced increases in acid solutions.

Power of reducing agents which are oxidised increases in basic solutions.
The Acid-Base Concept Proposed by Brnstedt and Lowry
- acids = proton donators, bases = proton acceptors
- valid for water and other protical solvents (e.g. liquid NH3)
- acid reaction: HX + H2O X- + H3O+

(H3O+ - oxonium ion, which will be solvatisated,
hydronium ion = [H3O 3 H2O]+)
- base reaction: M-OH M+ OH-
- autoprotolysis reaction of water: 2 H2O OH- + H3O+

K = 10-14, pH = -log [H3O+]
Acid anhydrides = compounds (oxides or metal cations) forming Brnstedt acids

first by the reaction with water
e.g. SO3 + 2 H2O H2SO4 + H2O HSO4- + H3O+

Al3+ + 7 H2O Al(OH2)63++ H2O [Al(OH2)5(OH)]2++ H3O+
Amphoteric compounds (ampholytes)

Compounds (mostly oxides), which can form acid and base ions:
Al(OH)3 + 3 H3O+ [Al(OH2)6 ]3+ (pH < 5)
Al(OH)3 + 3 OH- [Al(OH)6 ]3- (pH > 9)
Between pH 5 and 9 solid Al(OH)3 falls out.
The Acid-Base Concept Proposed by Lewis (1923)
- acids = electron pair acceptors, bases = electron pair donators
Lewis acid + Lewis base Lewis acid-base complex
Lewis acids: cations or electron shortage compounds,

which can attract electron pairs
BF3, AlH3, SO3, H+ , Fe 2+
Lewis bases: anions or compounds with unbounded electron pairs

F-, H2O, OH-, NH3, CN-
Lewis acid-base concept includes partially redox reactions.
Principle of hard and soft acids and bases (HSAB principle - by Pearson 1963)
Stability of the acid-base complex is high if there react

hard acids with hard bases or weak acids with weak bases.
hard acids: cations with small diameters, high positive charge and no non-bonded
electrons,
H+ , cations from s 1, s 2, s 2p1 and d10s2p2 elements
forming mainly ionic bonds

soft acids: cations with large diameters, low positive charge and non-bonded
electrons,
cations from transition metals
with d10s2 configuration (type B cations)
forming mainly covalent bonds
hard bases: anions with a central atom highly charged

and possessing a high electronegativity
soft bases: anions with a central atom low charged
and possessing a low electronegativity
(hard) Anions of F > O >> N, Cl >Br, H >S, C > I > P (weak)
Hard or soft properties of Lewis acids and bases can be found only experimentally.
Additionally strength of Lewis acids and bases must be considered!
Strong acids + strong bases give stable complexes every time (H+ + H- H2), but
selectivity is influenced by hard or soft character (Al 2S3 + HgO Al2O3 + HgS).

(3) Gisbert Gromann, Jrgen Fabian,

Lehrwerk Chemie, Lehrbuch 2 Struktur und Bindung Aggregierte Systeme und
Stoffsystematik,
(3) P.W. Atkins,

Physikalische Chemie,
2nd reprint of 1st edition, VCH Verlagsgesellschaft Weinheim, 1990
Chapter 3
Noble Gases
Overview About the Group
Group Helium Neon Argon Krypton Xenon Radon (Rn)

Members (He) (Ne) (Ar) (Kr) (Xe)
Atom 2 10 18 36 54 86
Number
Rel. Atomic 4.00 20.18 39.95 83.80 131.29 [222]
Mass (radio-
active)
Discovery 1895 1898 1894 1898 1898 1900
Ramsey Ramsey Ramsey, Ramsey Ramsey Dorn,
Rayleigh Rutherford,
Soddy
Percentage 0.000524 0.00182 0.9340 0.000114 0.000087 6 * 10-18
in air
[Vol.-%]
Electron configuration: sp 6(d 10) fully saturated electron shells

very poor or no reactivity
Industrial manufacturing: Rectification of air (Linde process)
Use: Inert gas in lamps and in high temperature processes

(Ne, Ar, Xe)
Balloon gas (He)
Medicine (Rn as source of 24 species)
Physical and Chemical Properties
Group Helium Neon Argon Krypton Xenon Radon

Members (He) (Ne) (Ar) (Kr) (Xe) (Rn)
melting point -272.1 -248.6 -189.4 -156.6 -111.5 -71
[C] (2.5 MPa)
boiling point -268.9 -246.0 -185.9 -152.9 -107.1 -61.8
[C] (4 He)
vaporization 0.092 1.86 6.28 9.68 13.70 18.02
enthalpy
[kJ/mol]
1st ionisation 24.58 21.56 15.76 14.00 12.13 10.7
energy [eV]
Low Temperature Properties of Helium
- lowest boiling and melting temperature of all substances

- cannot be frozen under atmospheric pressure (this needs 25.5 bars)
- Helium I (normal fluid) and Helium II (super fluid)
He(I) He(II) at -270.97 C (2.18 K)/1 bar for 4He
first at extreme low temperatures for 3He
- different physical properties of 3He and 4He
boiling points: 3.20/4.21 K
density: 0.08/0,14 g/cm
easy separation of isotopes possible
Ionisation potential of highest reactive elements:

O2 - 12.75 eV, similar to Xe
F2 - 17.4 eV, higher than Kr and Xe
Cl2 : - 12.9 eV, similar to Xe
Br2 : - 11.76 eV
First noble gas compound:

- clathrates (enclosed compounds, cage compounds)
- XePtF 6 by Barlett (1962, theoretically predicted by Pauling 1933)
Known noble gas compounds

- RnF 2, fluorides, oxides and oxifluorides of Xe, chlorides of Xe, KrF 2
- no compounds of He, Ne , Ar
The Air Rectification Process by Linde
Joule Thomson effect: Gases can be cooled by adiabatic expansion, if

temperature a is less than inversion temperature and
JT (Joule Thomson coefficient) is positive.
Joule Thomson parameter The Linde process

and inversion temperature for
different gases
compressed air
expanded air
(heating)
cooler cross flow
heat exchanger
air inlet
A, pA
(cooling)
throttle valve
(as the ideal gas)
compressor
E, pE
liqiud air
Process scheme:
1. Air in compressed to 200 bar (pA)
2. Compressed air is cooled to remove compression heat
3. Expanding of cooled compressed air followed
4. Expanded air cools compressed air
5. Air is compressed again (like 1.)
Cooling effect of Linde process:
A - E = JT * (pA pE) *(273.15/(273.15 + A))
Fractions of the technical rectification
further purification in additional rectification steps

Halogen Compounds of Noble Gases
Xe + F2
400
C , Ni tube XeF2
(colourless solid)
Xe + 2 F2
400 C , 0.6 MPa, Xe / F2 = 1: 5
XeF4
(colourless solid)
Xe + 3F2
200 250 C , 5 MPa, Xe / F2 = 1: 20
XeF6
(colourless solid)
Kr + F2
183 C , 20 mbar
KrF2
(colourless solid)
Molecular structures of XeF2 , XeF4 and XeF6
- reaction is possible after activation of fluorine (F2 2 F) by heat, UV radiation,

microwaves, electrical discharges or radiation
- stability: - increases with increasing atomic number of noble gas

atom (RnF 2 /XeF2 (stable) >> KrF2 (stable until 70 C) > ArF2 (not
reported))
- decreases with increasing atomic number of halogen
atom (XeF2 (stable) >> XeCl2 (unstable)> XeBr2 (unstable))
- decreases with increasing oxidation state of noble gas
atom (XeF2 > XeF4 > XeF6 (all stable, but increasing
formation enthalpy +164/+278/+361 kJ/mol), XeF8 (not reported))
- all noble gas halogen compounds have strong oxidation power

XeF2 : Cl- Cl2 , IO 3 - IO 4 , BrO 3 - BrO 4 - (all in aqueous solutions),
Fluorination of NO2 to FNO2 , reaction with F2 to XeF4 and XeF6
XeF4: Pt PtF 4 , Hg Hg2 F2
XeF6 : Hg HgF 2 , AuF 3 Au(V)
KrF2 : ClF 3 ClF 5 , Ag AgF 2 , Hg HgF 2 ,
[KrF]+ strongest known oxidation agent
7 KrF2 + 2 Au 2 [KrF][AuF 6 ] AuF 5 + Kr + F2
Oxygen Containing Compounds of Noble Gases
only known compounds: XeO 3 , XeO 4 , H4 XeO 6 ,

XeOF2 , XeO 2 F2 , XeOF4 , XeO3 F2 , XeO2 F4
Molecular structures of XeO 3 and XeO 4
Xenon(VI)-oxide (XeO 3 )
- preparation: XeF6 + 3 H2 O XeO 3 + 6 HF

3 XeF4 + 6 H2 O Xe + XeO 3 + 12 HF
- properties: colourless crystals,

soluble in water (> 1 mol/l),
weak acid (pKs = 10.5)
high oxidation power (Cl- Cl2 ,
Mn (II) Mn (IV))
explosive
Xenon(VIII)-oxide (XeO 4 )
- preparation: basic hydrolysis of XeO 3

XeO 3 + OH- HXeO 4 -
2 HXeO 4 - + 2 OH- XeO 46-+ Xe + O2 +2 H2 O
- properties: XeO 4 yellow liquid (< - 40 C)/colourless gas,

XeO 4 6- yellow solutions
XeO 4 explosive above 40 C
strong oxidation power (ClO 3 - ClO 4-, Cr3+ Cr2O7-, Mn2+
MnO4 -,(IO 3 - IO 4-)
Oxiflouride Compounds
- preparation: deep temperature hydrolysis of XeF4 ,

reaction of xenon fluorides with xenon oxides
- properties: colourless crystals, which can be hydrolysed,

poor stability

Lehrbuch der anorga nischen Chemie

Stoffsystematik,
(3) P.W. Atkins,

Chapter 4
Hydrogen
Overview
- discovered 1766 by Cavendish

- lightest element
- third most common element by atom percentage,
ninth most common element by mass percentage
- occurs in nature mostly as oxide (water H2 O)
Hydrogen isotopes
Name protium H deuterium D tritium T

atom core 1 proton 1 proton + 1 proton +
composition 1 neutron 2 neutrons
rel. atomic 1.0078 2.0141 3.0160
mass
natural 99.9855 % 0.0145 % 10-15 %
percentage
Electron configuration: s1
needs to spent or to accept one electron
occurs in elementary form as diatomic H2
ortho and para hydrogen
spins of protons - o-H2 p-H2 + 0.08 kJ/mol

electron shell - ratio at 25 C: 75/25
- separation by adsorption on
atom cores alumina at 20.4 K and 50 mbar
ortho-hydrogen para-hydrogen
- differences in physical properties
para-hydrogen (melting and boiling points, c p,
percentage of ortho-hydrogen [%]
percentage of para-hydrogen [%]
vapour pressures)
ortho -hydrogen
absolute temperature
Chemical properties
Homolytic dissociation energy (H2 2 H): 436.2 kJ/mol
catalytic activation by high dispersed transition metals
(e.g. Pt, Pd)
Heterolytic dissociation energy (H2 H + + H-): 1675 kJ/mol
Oxidation enthalpy (2 H2 + O2 2 H2O): -572.04 kJ/mol
Reduction enthalpy (Ca + H2 CaH2): -184 kJ/mol
Manufacturing and Use of Elementary Hydrogen
Industrial manufacturing: world production 35 mill. tons/year (1990)
Steam cracking/Steam reforming

of oil and natural gas (>90 %)
CH4 + H2O CO + 3 H2
(700-830 C, 40 bar, Ni catalyst)
Coal gasification
C + H2O CO2 + H2
Water shift reaction
CO + H2O CO2 + H2
Synthesis gas is a mixture of CO and H2 (traces of
CO2, and H2O)
Chlorine alkali electrolysis

NaCl + H2O NaOH + 1/2 Cl2 + 1/2 H2
Laboratory manufacturing: Reaction of non-noble metals (Zn, Ca, Mg)

with diluted acids (HCl, H2SO4, HNO3)
M + 2 H+ M2+ + 2 H M2+ +H2
(2 H = status nascendi
= high reactive atomic hydrogen)
Reaction of metallic Al or Si with hot NaOH

giving aluminates and silicates and H2
Use: Ammonia production

(Haber Bosch process, N2 + 3 H2 2 NH3)
Organic chemistry (Hydrogenation, reducing agent)
Inorganic chemistry (HCl synthesis,
reducing agent for metal manufacturing)
Food industry (fatty acid hydrogenation)
Fuel Cell Technology
Binary Hydrogen Compounds Ionic Compounds
General:
- formed with elements of the 1st and 2nd main group by direct synthesis from the
elements
- nomenclature:
[Name of the metal] ([number of H atoms]) hydride
e.g. Magnesium(di)hydride MgH2
Structure and Properties:
- bond between the metal and the hydrogen is primarily ionic
- metal ions possess positive charge, hydrogen is charged negatively
- exothermic compounds with salt crystal structures, high decomposition

temperatures (300-1000 C), electrical conductivity in molten state
- solution in water under decomposition to hydroxides and hydrogen
- strong reducing agents, industrial use for manufacturing pure elements (e.g. LiH,
NaH, CaH2)
- exception: BeH2 is a typical covalent compound
Reactions: with halogens to metal halogenides + hydrogen

e.g. CaH2 + X2 MeX2 + H2
with oxygen to oxides and water

e.g. CaH2 + O2 CaO + H2O (500 C)
with nitrogen to nitrides and hydrogen

e.g. 3 CaH2 + N2 Ca3N2 + 3 H2 (500 C)
with carbon to carbides and hydrogen

e.g. CaH2 + 2 C CaC 2 + H2 (>700 C)
Binary Hydrogen Compounds Metallic Compounds (1)
General:
- formed with transition metals and the metals of the III.-VI. main group
Preparation:
- by direct synthesis from the elements

giving non-stochiometric compounds
solution hydride
phase phase
hydrogen pressure
mixed phase
(solution + hydride)
plateau region
hydrogen uptake (mol H/mol metal)
- by reaction of halogenides with LiH, NaBH2 or LiAlH4

EHal n + n H- EHn + n Hal -
Stability:
- IIIb and IVb groups: exothermic compounds, stable at room temperature

- Vb group and CrH: endothermic compounds, meta-stable
- VIb-VIIIb groups: very unstable or not discovered
- Ib, IIb and IIIa-VIa groups: endothermic compounds, stable only at low
temperatures
- stability decreases with increasing hydrogen content
(VH stable at room temperature, VH2 decomposes)
Group IIIb IVb Vb VIb VIIb VIIIb Ib IIb

Hydrogen metal =31 =2 =2 =22 n.d. =22 1 2
ratio x of the
compound EHx
Stability increase Hydrogenation
catalysts
1 including lanthanoides and actinoides
2 only known from Cr, Ni (at high pressures) and Pd
n.d. not discovered
Binary Hydrogen Compounds Metallic Compounds (2)
Structure and Physical Properties:
- inlay compounds no changes in the metal lattice structure
- hydrogen atoms occupy lattice gaps, they can move inside the gap
- presence of cationic and anionic hydrogen
- conductors using free electrons
- in gas phase linear molecules HMH
Reactions and Use:
- reaction with water under decomposition to hydroxides and hydrogen
- manufacturing of high purity metals
- hydrogen storage
Binary Hydrogen Compounds Covalent Compounds (1)
General:
- formed with non-metallic elements of the III.-VII. main group
- high industrial importance
Preparation:
- by direct synthesis from the elements (e.g. Haber Bosch process for ammonia)
- reaction of metal compounds of elements of the III.-VII. main group with acids (e.g.
CaF2 + H2SO4 CaSO4 + 2 HF industrial process)
Structure:
planar triangle tetrahedron pyramidal planar angled

(IIIa group (IVa group (Va group (VIa group
elements) elements) elements) elements)
- hydrogen possesses positive charge for H-Hal, H2O-H2Se, NH3, CH4

- multiple centred bonds (coordination number of H = 2, equal bond length) in Be-H
and B-H compounds via anionic hydrogen bridging bonds (polymerisation)
- association of hydrides from elements of the 2 nd period

via cationic hydrogen bridging bonds (longer than covalent bonds)
(HF) x (solid) (HF) 6 (gaseous)

Physical and Chemical Properties:

- non-conductors
- high volatility except hydrocarbon compounds from N, O and F (much higher
melting and boiling points because of cationic hydrogen bridging bounds) and from
B (dimerisation)
melting points boiling points
period period
- exothermic and stable compounds (without higher periods)

- solubility in water
o H-Hal: high solubility with strong acid reaction
o H2X (VIa group): high solubility with weak acid reaction
o NxHy: high solubility with strong basic reaction
o H3X (Va group since P): low solubility with low basic reaction
o H4X (IVa group): no solubility
o (H3B)x: no solubility
dissociation 2 EHn EHn+1 + + EHn-1-
- well soluble in ethers

- use as polar solvents: H2O, NH3 (liquid), HF (liquid)
use as non-polar solvents: higher hydrocarbons (C = 612)
- reducing power (EHn + (n+p)/2 X2 n HX2 + EXp)

F2 > O2 > Cl 2 >Br 2 , correlates to electronegativity and to normalised
electrochemical potentials
Higher Hydrogen Compounds

- molecules with more than one single or multiple bonded element atoms
(especially with elements of 2nd period)
Reactions
- protonation/deprotonation (Va-VIIIa group elements)
H+ + H2O H3O+
NH3 + H3O+ NH4+ + H2O
NH3 NH2- + H+
- accepting hydride ions (IIIa group elements):

BH3 + H- BH4-
AlH3 + H- AlH4-
Heavy and Super-heavy Water
H2 O D2 O T2 O
light water heavy water super-heavy
water
rel. molecular mass 18.02 20.03 22.03
density (25 C) [g/cm] 0.997 1.104 1.214
maximum density [g/cm] / 1.000/3.98 1.106/11.23 1.215/13.4
Temperature of density
maximum [C]
melting point [C] 0.000 3.81 4.48
boiling point [C] 100.00 101.42 101.51
dissociation constant pKW (25 14.000 14.869 15.215
C)
Toxicity low (salt-free) high radioactive
Industrial manufacturing : Electrolysis of used technical electrolyte

solutions
enrichment of D2 during the end of the
process because of lower reaction rate
Use: Nuclear industry,

Studies on reaction mechanisms
(H-D exchange)


Stoffsystematik,
(3) P.W. Atkins,

Chapter 5
Halogens
Group Fluorine Chlorine Bromine Iodine Astatine

Members (F) (Cl) (Br) (I) (At)
Atom Number 9 17 35 53 85
Rel. Atomic 19.00 35.45 79.9 126.90 209.99
Mass
Discovery 1886 1774 1826 1811 1940
Moissan Scheele Balard Courtois Corson,
McKenzie,
Segr
Percentage on 0.06 0.11 6 * 10-4 5 * 10-5 3 * 10-24
earth [Mass- (radio-
%] active)
melting point -219.62 -101.00 -7.25 113.60 300
[C]
boiling point -188.13 -34.06 58.78 185.24 335
[C]
state at room colourless - yellow- dark brown violet solid
temperature weak green liquid crystals
(25 C) yellow gas gas with
and 1 bar metallic
brilliance
Electron 4.0 3.0 2.8 2.5 2.2
negativity
valence -1 -1+7 -1+7 -1+7 -1+7
numbers in
compounds
Reducing
Power
Oxidation
power
Electron configuration: sp 5(d 10) need of accepting one electron

or loosing 7 electrons for full saturation of electron
shells
very high up to extreme reactivity
occurs in nature only in compounds
in gas phase diatomic molecules X2
Manufacturing and Use of Elementary Fluorine
Fluorine is the elements with the highest electronegativity (4.0).

It is the element with the highest reactivity. Elementary fluorine cannot be formed
by any chemical reaction.
Natural Sources:
fluorspar CaF2 (main source, 5 * 106 t/year)
fluorapatite 3 Ca3(PO4)2 CaF2 (with 24 mass-% F)
cryolite Na3 AlF6
Manufacturing in industry:
1. Conversion of fluorspar to hydrofluoric acid
CaF2 + H2SO4 CaSO4 + 2 HF
2. Electrolysis of hydrofluoric acid to fluorine in water-free molten KF 2 HF
(melting temperature: 72 C)
2 HF H2 + F2
Process data
voltage: 8-12 V
current: 4-15 kA
current density: 0.5-0.15 A/cm
temperature: 70-130 C
yield 90-95 %
(relative to the
current consumed)
3. Purification of F2 by freezing out un-reacted HF at -100 C
Properties and Application:

- high toxic in elementary form (essentially as ionic fluoride)
- one of the strongest oxidation agents (H2 O + F2 2 HF + 0.5 O2)
- heavy reaction with most of the other elements
even at room temperature (except He, Ne, Ar)
- used for industrial synthesis of UF6, SF6, CF4 and fluorographite (electrodes in
batteries)
- surface fluoridation (Teflon)
Manufacturing and Use of Elementary Chlorine
Natural Sources:
sodium chloride NaCl
(main source, from mining or from seawater, 170 * 106 t/year, purification and
enrichment up to 99 %)
potassium chloride KCl (mostly used as fertilizer)
other natural salts: KMgCl 3 6 H2O,
MgCl 2 6 H2O,
KMgCl(SO4) 3 H2O
1. Electrolysis of NaCl brines

(2 H2O + 2 NaCl H2 + 2 NaOH + Cl 2)
Restrictions to the process:
- prevention of formation of hypochlorite in the solution
(2 OH- + Cl 2 OCl - + Cl -)
- suppressing of contact between H2 and Cl 2
( 2 HCl danger of explosions)
- mercury process (40 % of world production)
- diaphragm process (40 % of world production)
- membrane process(20 % of world production)
2. Electrolysis of concentrated hydrochloric acid
2 H+ + 2 Cl - H2 + Cl 2
3. Thermal oxidation of hydrogen chloride (Deacon process)
4 HCl + O2 2 H2O + 2 HCl + 2 Cl 2
catalyst: CuCl 2 (Deacon process 350 C)
or MnO2 (Weldon process)
Properties:
- yellow green, suffocative smelling gas
- soluble in water (0.0921 mol /l = 6.6 g/l)
- high toxic in elementary form (essentially as ionic chloride)
- high reactivity, especially with non-noble metals and hydrogen
(but less than fluorine)
- reactivity is increased by adding small amounts of water
(forming of traces of ClO- initiators)
- high oxidation power (less than fluorine)
Application:
- synthesis of organic chemicals (mainly vinyl chloride)
- leaching agent in paper and pulp industry
- inorganic chemicals, water treatment, cleaning and sanitation
The Mercury Process for Manufacturing Chlorine
General:
- separation of chloride oxidation and hydrogen reduction
- Step 1: Electrolysis of NaCl gives sodium solved in mercury (amalgam) and
gaseous chlorine.
Anode: Cl- 0.5 Cl 2 + e - ( = 1.24 V)
Cathode: x Hg + Na+ + e - NaHgx ( = -1.66 V)
- Step 2: Decomposition of amalgam to Hg (recycling), NaOH and H2
NaHgx +H2O 0.5 H2 + NaOH + x Hg
Process parameters cell voltage: 4.2 V

current density: 8-15 kA/m
temperature: 80 C
NaCl concentration
start: 310 g/l
end: 260-280 g/l
electrochemical yield: 94-97 %
Advantages:
- pure 50 % sodium hydroxide solution without evaporation
- high purity chlorine gas
Disadvantages:
- need of higher voltage and energy compared to the diaphragm process
- stronger brine purification requirements
- care on preventing emissions of mercury
Halogen Oxygen Compounds The Complete Reaction Network
Example: Chlorine
oxidation state
The Diaphragm Process for Manufacturing Chlorine
General:
- separation of chloride oxidation and hydrogen reduction
by an asbestos membrane
- Reactions:
Anode: Cl- 0.5 Cl 2 + e - ( 0= 1.36 V)
Na + + OH- NaOH
Cathode: H2O + e -
H2 + OH-
( 0 = 0 (pH = 0)/-0.828 V (pH = 14))
NaCl Na + + Cl -
Process parameters cell voltage: 3.0-4.15 V

current density: 2.2-2.7 kA/m
final NaCl concentration: 170 g/l
final NaOH concentration: 12-16 %
Diaphragm functionalities:
- hindering of gas transport between the chambers - suppressing of contact between
H2 and Cl 2 (but permeability for dissolved Cl 2)
- hindering of OH- transport to the anode
Advantages:
- less requirements to NaCl purity
- lower voltage and energy consumption
Disadvantages:
- need of additional separation steps for NaOH and NaCl,
and of an evaporation step to enrich NaOH
- oxygen content in the chlorine
- care on preventing emissions of asbestos
The Membrane Process for Manufacturing Chlorine
General:
- separation of chloride oxidation and hydrogen reduction by a Nafion membrane
- Reactions:
Anode: Cl- 0.5 Cl 2 + e - ( 0= 1.36 V)
Na + + OH- NaOH
Cathode: H2O + e -
H2 + OH-
( 0 = 0 (pH = 0)/-0.828 V (pH = 14))
NaCl Na + + Cl -
Process parameters
cell voltage: 3.15 V
current density: 2-3 kA/m membrane materials
final NaOH concentration: 35 %
current yield: 95 %
with respect to NaOH
Properties of the membrane:

- thickness: 0.2 mm
- ion-conductible, but non-permeable for the brine
Advantages:
- pure NaOH without NaCl impurities
- lower voltage and energy consumption than the mercury process
- no use of mercury or asbestos, ecological most favoured process
Disadvantages:
- high purity requirements to NaCl
- low final concentration NaOH
and of an evaporation step to enrich NaOH
- oxygen content in the chlorine
- high costs and short lifetime of membranes
Manufacturing and Use of Elementary Bromine
Natural Sources:
seawater (main source)
residual solutions from potash (K2CO3) industry
Chlorine extraction of bromide ion containing brines (500000 t/a)
(2 Br- + 2 Cl2 Br2 + 2 Cl-)
- Cold debromination
1. acidification of seawater to pH = 3.5
with sulfuric acid (H2SO4)
2. extraction of formed bromine by blowing out with air
3. purification by adsorption with soda solution (a) and desorption with
H2SO4 and steam (b)
3 Br2 + 6 OH- 5 Br- + BrO 3- + 3 H2O (a)
5 Br- + BrO 3- + 6 H+ 3 Br2 + 6 H2O (b)
- Hot debromination (major process)
1. Counter-current extraction of brines with a mixture of steam and Cl2
at 80 C
2. Condensation of the steam containing Br2, Cl2 and H2O
3. Purification by distillation
Properties:
- brown high volatile liquid
(melting point: -7.25 C, boiling point 58.78 C)
- soluble in water (0.2141 mol /l = 34.2 g/l)
- high toxic in elementary form
- quite high reactivity, less than fluorine and chlorine
- reactivity is increased by adding small amounts of water
(forming of traces of BrO - initiators)
- high oxidation power (less than fluorine and chlorine)
Application:
- synthesis of organic chemicals (mainly for medicine)
- manufacturing of flame retardants (in decrease)
- inorganic chemicals
Manufacturing and Use of Elementary Iodine
Natural Sources:
- occurs in nature only in small concentrations
as iodide (I-) or iodate (IO3-)
- industrial sources:
residual solutions from Chilean niter (NaNO3) industry
(main source, containing mainly IO3-),
brines from crude oil and natural gas production
1. from residual solutions of Chilean niter production (50 %)
- acidification of brines with H2 SO3
(treatment with gaseous SO2) reduction of IO3- to I-
(HIO3 + 3 H2 SO3 HI + 3 H2SO4)
- comproportionation of iodine hydrogen with further
iodine acid
(5 HI + HIO3 3 I2 + 3 H2O)
- purification by sublimation of the crude iodine
2. from brines from crude oil and natural gas production (50 %)
- similar process like for bromination
extraction with Cl 2/H2 SO4 blow out of iodine with air
purification by reduction with SO2 and re-oxidation with Cl 2 or by
adsorption and desorption on anion exchangers
Properties:
- solid grey-black crystals with metallic brilliance and a high tendency to sublimate
(melting point: 113.6 C, boiling point: 185.2 C)
- molten iodine conducts electricity
- rather low solubility in water (0.0013 mol /l = 33.88 g/l),
high solubility in iodide solutions and in organic solvents
- toxic in elementary form, but essentially as ionic iodide
- rather low reactivity, heavier reactions especially with P, Al, Fe and Hg, less
tendency to react with hydrogen
- can be used as an oxidation agent and a reduction agent
Application:
- catalysts and very pure metals (van Arkel process for Zr and Ti via tetraiodides,
used in the stereospecific polymerisation of butadiene)
- disinfections
- pharmaceutical industry, food and feedstuff additives, agriculture
- iodine impregnated activated carbon for Hg adsorption from waste gases
- photography and rain cloud formation (AgI)
- polyamide 6.6 (nylon) stabilisation
Properties of Halogen Compounds
In compounds fluorine has an oxidation number of 1 every time. Chlorine, bromine and
iodine can reach oxidation numbers from 1 to + 7, whereby the electropositive character
increases with the period number.
Metal halogenides
- formation directly from the elements

(partially very heavy reactions, even Au and Pt are attacked)
- Solubility in water and other polar solvents:
high for salts formed with elements of the Ia and IIa groups
low for salts formed with the heavy transition metals
and the noble metals
- fluoride salts have partially inversed solubility properties compared to the
other halogens
- neutral salts F-, acid salts [F-H-F]- (MeF HF adducts)
Covalent halogen compounds with non-metallic elements
- formation from reaction of hydrocarbon compounds with fluorine

(partially very heavy to explosive reactions) or by substitution reactions
- highest coordination numbers of positive core atom for fluorine compounds, e.g.
SF6, PF6-
- solubility in water increases with the ionic character of bonds in the molecule
- high volatility, low boiling temperatures especially in case of highly halogenated
compounds
Hydrogen Compounds of the Halogens
Formula HF HCl HBr HI
Name of the Hydrogen Hydrogen Hydrogen Hydrogen

poor fluoride chloride bromide iodide
compound
Formation -271 -92 -36 +26
enthalpy B H0
[kJ/mol]
0 (2 X-/X2) +3.05/+2.87 +1.63/+0.42 +1.06/+1.06 +0.54/+0.54
[V] (pH=0/14)
Reducing
power
Oxidation
power
state at room colourless gas colourless gas colourless gas colourless

temperature with with with furning liquid
(25 C) sticking smell, sticking smell, sticking smell with
and 1 bar toxic toxic toxic sticking smell
toxic
melting point -83 -114 -87 -35
[C]
boiling point +20 -85 -67 +26
[C]
Name of the hydrofluoric hydrochloric hydrobromic hydroiodic acid

aqueous acid acid acid
solution
pK s +3.2 -6.1 -8.9 -9.3
solubility unlimited 507 612 425
[l/l H2O]
Manufacturing and Use of Hydrogen Fluoride
Conversion of fluorspar CaF 2 (Bayer Process)
CaF 2 + H2SO4 CaSO4 + 2 HF (200-250 C)
Manufacturing in the laboratory:

Heating of acid fluorides of type MF HF (e.g. M = K)
MF HF MF + HF
Properties:
- highest bonding energy of all hydrogen compounds
- hygroscopic liquid (melting point: - 83.36 C,
boiling point: 19.51 C)
- soluble in water forming hydrogen fluoric acid (H3O+F- - pKs = 3.2)
- occurs in gas phase as (HF)6, at temperatures > 90 C as HF
- forms neutral salts MF x and acid salts MF x (HF)n
Application:
- manufacture of inorganic fluorides (AlF 3, BF 3, UF 6, NH4F)
- manufacture of organic fluorocompounds
(esp. fluorohalogenhydrocarbons)
- etching and polishing in the glass industry
- manufacture of semiconductors
NOTE: Hydrogen fluoride and hydrogen fluoric acid attack glass and
quartz (SiO 2 + 4 HF SiF 4 (g) + 2 H2O)! Store them only in Pb, Pt or
in paraffin, PE, PP or Teflon bottles!
Industrial Important Fluorides
Aluminium Fluoride (AlF 3 )

- manufacture: Lurgi Process
2 Al(OH)3 Al2 O3 + 3 H2 O (300-400 C)
Al2 O3 + 6 HF 2 AlF 3 + 3 H2 O (400-600 C)
Chemie Linz AG process
2 Al(OH)3 + H2 SiF 6 2 AlF 3 + SiO 2 + 4 H2 O (100 C)
- use: flux in the aluminium industry
Sodium Aluminum Hexafluoride (Cryolite Na3 AlF 6 )

- manufacture: 6 NH4 F + 3 NaOH + 2 Al(OH)3
Na3 AlF 6 + 6 NH3 + 6 H2 O
- use: electrolytic manufacture of aluminium
Alkali Fluorides (NaF, KHF 2 , NH4 F HF)

- manufacture: NaOH + HF or H2 SiF 6
- use: NaF water fluoridation
KHF 2 frosting agent in glass industry,
synthesis of F2
NH4 F oil extraction
Hexafluorosilicates (M2 SiF 6 )

- manufacture: 2 MCl + H2 SiF 6 M2 SiF 6 + 2 HF
- use: wood protection
Na2 SiF 6 - water fluoridation
Uranum Hexafluoride (UF 6 )

- manufacture: UO2 + 4 HF UF4 + 2 H2 O
UF4 + F2 UF6
- use: separation of 235 U and 238 U in nuclear technology
Sulfur Hexafluoride (SF6 )

- manufacture: S + 3 F2 SF6
- use: protective gas in high voltage installations
Boron Trifluoride (BF 3 ) and Tetrafluoroboron acid (HBF 4 )

- manufacture: (1) Na2 B4 O7 + 6 CaF2 + 7 SO 3
4 BF3 + 6 CaSO4 + Na2 SO4
(reaction is carried out in conc. H2 SO4 )
(2) HBO3 + 3 HF BF3 + 3 H2 O
HBO3 + 4 HF HBF 4 + 3 H2 O
(reactions are carried out in conc. H2 SO4 )
- use: Friedel-Crafts catalyst in organic chemistry (BF 3 )
galvanic metal deposition, fluxes, flame retardants
Manufacturing and Use of Hydrogen Chloride
(1) byproduct of synthesis of organic and inorganic chemicals
(main source 90 % of world market)
e.g.: - manufacturing of chlorohydrocarbons
(radicalic substituation)
- reaction between amines and phosgene
forming isocyanates
R-NH2 + COCl 2 RN=C=O + 2 HCl
- substitution of chlorine by fluorine
in organic molecules
R-Cl + HF R-F + HCl
- manufacturing of phosphoric acid and of its esters
- manufacturing of high surface silica
by flame hydrolysis (SiCl 4, H2, O2)
2 H 2 + O2 H2O
SiCl 4 + 2 H2 O SiO2 + 2 HCl
(2) direct formation from the elements in a flame of 2000 C
(Daniell burner - 8 % of world market)
H2 + Cl 2 2 HCl
(3) byproduct of NaHSO4 formation from NaCl and H2SO4
(Leblanc process/Hargreaves process - 1-2 % of world market)
SO2 + H2O + 0.5 O2 H2SO4 (pre-process)
NaCl + H2SO4 NaHSO4 + HCl
NaHSO4 + NaCl Na2 SO4 + HCl
Manufacturing in the laboratory:

2 NaCl + H2SO4 2 Na2 SO4 + HCl
Properties:
- well soluble in water (20 mol/l), short chain alcohols and ethers
- traded concentrated hydrochloric acid is 38 % HCl in H2O
- high oxidation power (e.g. forming chlorides from the elements)
Application:
- synthesis of chlorine containing organic compounds (addition reactions)
- neutralisation reactions
- acid hydrolysis reactions
- regeneration of ion exchangers
- polar solvent
- manufacturing of chlorine (electrolysis/modified Deacon process) and chlorine
dioxide
Amount of HCl exceeds demand.
Manufacturing and Use of Hydrogen Bromide and Iodide
HBr HI
Manufacturing of (1) from the elements (1) from the elements
hydrogen H2 + Br 2 2 HBr H2 + I2 2 HI
halogenide: (350 C, Pt catalyst) (500 C, Pt catalyst)
(2) Byproduct of organic (2) hydrazine + iodine
bromine substitution N2H4 + I2 4 HI + N2
reactions
Manufacturing of MOH + HBr MBr + H2O MOH + HI MI + H2O
halogenides: or directly from the elements
Industrial NaBr, use in oil industry TiI4 catalysts
application: CaBr 2,
ZnBr 2 NaI, pharmaceutical purposes
KI
LiBr drying agent for air photography
AgI induction of rain
KBr photography
NH4Br
Interhalogen Compounds
Electronegative partner F Cl Br
(valency = -1)
Electropositive Valency
partner
Cl +1 ClF
+3 ClF3
+5 ClF5
+7 -
Br +1 BrF BrCl
+3 BrF3 -
+5 BrF5 -
+7 - -
I +1 IF ICl IBr
+3 IF3 (ICl 3)2 -
+5 IF5 - -
+7 IF7 - -
Structure:
AB3 AB5 AB7
Lewis acids
Properties:
- synthesis from the elements (variation of reactant ratios and
reaction conditions)
- similar to elements A2 and B2
- high fluoridation and oxidation activity
(increase with number of fluorine atoms, Cl > Br > I with respect to central atom)
- disproportionation reactions of middle compounds,
e.g. 5 IF3 I2 + 3 IF5
- high toxicity
Application:
- ClF, ClF3, BrF3 and IF5 are used as industrial fluoridation agents (tons per year, e.g.
UF6 manufacturing)
- ClF3 adducts with ammonia and hydrazine as fuel for rockets
Halogen Oxides Overview
Valency F Cl Br I
-1 OF2 - - -
Oxygendifluorid1 ,
(F-O-O-F)
Dioxygendifluorid 1
+1 - Cl2 O (Br2 O) -
+2 - (ClO, Cl2 O2 ) - -
+3 - (Cl2 O3 ) (Br2 O3 ) I4 O9 (+3 and +4)
+4 - ClO 2 - I2 O4
(Cl2 O4 )
+5 - - (Br2 O5 ) I2 O5
+6 - (ClO 3 ), Cl2 O6 - I2 O6
(+5 and +7)
+7 - Cl2 O7 - I2 O7
1
NOTE: Compounds should be named as oxygen fluorides, NOT as oxides!
Grey Fields technical importance, () not stable under standard conditions
Properties:
- metastable endothermic explosive compounds compounds (without I2O5)
- ionic character increases Cl < Br < I oxides
- high oxidation activity (increase Cl < Br < I)
- in situ utilisation
- disproportionation reactions of middle compounds
Application:
- leaching agents
- purification agents (oxygendonators)
- fireworks
Halogen Oxides Synthesis and Use
General synthesis:
- formation from the elements under consumption of energy
(electrical discharges at deep temperatures)
- extraction of a water molecule from the corresponding acids
- dis- and com-proportionation reactions
Special synthesises:
a) Dihalogenmonoxides X2O
F2O: - hydrolysis of fluorine in basic solutions
2 F2 + 2 OH- 2 F- + OF2 + H2O
Cl2O: - formed by 2 Cl 2 + 3 HgO HgCl 2 HgO + Cl 2O
- use for synthesis of hypochlorites and chlorine isocyanates
- leaching agent for textiles and wood
Br2O: - 2 Br 2 + 3 HgO HgBr 2 HgO + Br 2O ( < -60 C)
b) Halogenmonoxides (XO) n
ClO: - product of photolytic oxidation of Cl atoms in
higher layers of the atmosphere
- radicalic properties (one free electron)
- destroys ozone layer
(ClO Cl + O, Cl + O3 ClO + O2)
c) Higher halogen oxides

ClO2: - ER process by Erco, SVP process by Hooker
(both starting from sodium chlorate)
2 HClO3 + SO2 2 ClO2 + H2 SO4 (in 3-5 mol/l H2SO4)
alternatively: NaClO3 + HCl Cl2 + ClO2
- Munich or Kesting process:
1. Electrolysis of NaCl without cell separation
NaCl + 3 H2O NaClO3 + 3 H2
2. Reaction of chlorate solution with HCl
2 NaClO3 + 2 HCl 2 ClO2 + Cl 2 + 2 H2O + NaCl
- 2 NaClO2 + Cl 2 2 ClO2 + 2 NaCl
- Transport as sodium chlorite or stabilised with pyridine
- Use as a leaching agent for wood pulp (no chlorolignin
formation) and disinfections agent for potable water
(less chlorination degree than Cl 2)
I2O5: - Thermal treatment of iodine acid (200 C)
2 HIO3 I2 O5 + H2O
Halogen Acids and Their Salts Overview
Nomenclature:
HXO hypohalogenous acid XO- - hypohalogenite
HXO2 halogenous acid XO2- - halogenite
HXO3 halogenic acid XO3- - halogenate
HXO4 perhalogenic acid XO4- - perhalogenate
Acids:
protons are bonded with an oxygen atom
Increase of acid strength

Valency F Cl Br I
-1 (HOF) - - -
+1 - (HClO) (HBrO) (HIO)
Ks = 2.9 * 108 Ks = 2.1 * 10-8 Ks = 2.3 * 10-11
+2 - - - -
+3 - (HClO 2 ) (HBrO 2 ) (HIO 2 )
Ks = 1.1 * 102
+4 - - - -
+5 - (HClO 3 ) (HBrO 3 ) HIO 3
Ks = 5.0* 102 Ks ~ 1
+6 - - - -
+7 - HClO 4 (HBrO 4 ) (HIO 4 )
Ks = 1010 (H5 IO 6 )
(H7 I3 O14 )
Grey fields technical importance, () only stable in aqueous dilution,
H5 IO6 ortho-periodic acid, H7 I3 O14 tri-periodic acid
Base Anions:
Increase of basic strength

Valency F Cl Br I
-1 (OF-) - - -
+1 - ClO - (BrO -) (IO -)
+3 - ClO 2 - BrO 2 - (IO 2 -)
+5 - ClO 3 - BrO 3 - IO 3 -
+7 - ClO 4 - BrO 4 - IO 4 -
H5-n IO6n-
H7-n I3 O14n-
Hypohalogeneous acids (HOX) and Their Salts (XO-)
HOF: - formation at 40 C: F2 + H2 O HOF + HF

- decomposition in the gas phase and in weak basic solutions:
2 HOF 2 HF + O2
- decomposition in neutral and acid solutions:
HOF + H2 O HF + H2 O2
HOCl/OCl- : - formation reactions:

(1) in water: Cl2 + H2 O HCl + HClO (K << 1)
(2) 2 Cl2 + 3 HgO + H2 O HgCl2 HgO + 2 HOCl
(3) in basic solutions: Cl2 + 2 OH- Cl- + OCl- + H2 O
(industrial manufacturing with NaOH in solution at 40 C
or with Ca(OH)2 for solid salt Perchloron process)
(4) Olin /ICI /Thann and Pennwalt processes:
Ca(OH)2 + 2 NaOCl + Cl2 +11 H2 O
Ca(OCl) 2 NaOCl NaCl 12 H2 O
+ Ca(OCl)Cl Ca(OCl) 2 2 H2 O
+ 2 NaCl + 10 H2 O
(5) PPG process: Ca(OH)2 + 2 HOCl Ca(OCl)2 +2 H2 O
(6) electrolysis of seawater or brines in diaphragmless cells
(small industrial consumers)
- acid not stable in higher concentrations ( in situ use)
- stable salts: LiOCl, Ca(OCl)2 , Sr(OCl)2 , Ba(OCl) 2 , NaOCl
- commercial use for bleaching, for disinfections (e.g. water in swimming
pools), neutralisation of poison gases and hydrazine manufacture
- use as chlorinated trisodium phosphate ([Na3 PO4 11 H2O]4 NaOCl)
as cleaning agent in households and industry, especially in the USA
- high oxidation power of the acid by formation of intermediate atomar
oxygen (HClO HCl + O),
oxidation potential 0 (HClO/Cl-) = + 1.49 V
- very weak acid (K s = 2.9 * 10-8 ), hydrolysis of salts
- decomposition (catalysed by light)
(1) acid solution: 2 HClO (aq) 2 HCl (aq) +O2
(2) basic solution: 3 HClO 2 HCl + HClO 3
HOBr/OBr- : - formation and decomposition reactions similar to HOCl

- disproportionation in water 2 BrO - Br- + BrO 3 -
- only alkali salts are stable until 0 C
HOI/OI- : - formation reactions:

(1) 2 I2 + 3 HgO + H2 O HgI2 HgO + 2 HOI
(2) in basic solutions: I2 + 2 NaOH NaI + NaOI + H2 O
- very poor stability of acid, poor stability of salts
- disproportionation: 5 HIO HIO 3 + 2 I2 + 2 H2 O
Halogeneous acids (HOX2) and Their Salts (XO2-)
HClO2/ClO2-: - acid decomposes 5 HClO2 4 ClO2 + HCl + 2 H2O

- salt formation: 2 ClO2 + 2 MOH
MClO2 + MClO3 + H2O
2 ClO2 + 2 MOH + H2 O2
2 MClO2 + O2 + H 2O
- salts are relatively stable
- high oxidation power, partially explosions
- only industrial importance of NaClO2 formed by
2 ClO2 + 2 NaOH + H2O2 (excess)
2 NaClO2 + O2 + H2O,
used for ClO2 manufacture for small-scale users
BrO2-: - exists only as salts

- formation of salts: (1) disproportionation of BrO-
2 BrO- Br- + BrO2-
(2) comproportionation
(solid reaction in absence of
water) Br - + BrO3- 2 BrO2-
- decomposition in acid solutions, forming bromine
HIO2/IO2-: - both very unstable, no chemistry is known

Halogenic acids (HOX 3) and Their Salts (XO3-)
HClO 3 /ClO 3 -: - formation: (1) 2 HClO + ClO - ClO 3 - + 2 HCl

(disproportionation of HClO
in acid solutions)
(2) 3 Cl2 + 6 OH- ClO 3 - + 5 Cl- + 3 H2 O
(3) Electrolysis of NaCl without cell separation
NaCl + 3 H2 O NaClO 3 + 3 H2
(technical process)
- acid is stable up to 40 %
- very strong oxidation agent in acid solution
e.g. ClO 3 - + 5 X- + 6 H+ XCl + 2 X2 + 3 H2 O
- less oxidation power of basic salt solutions
(in contrast to solid salts)
- industrial manufacture of Na salts by reaction (3) and
metathesis of NaClO 3 with KCl ( NaCl + KClO 3 )
- commercial use of NaClO 3 :
mainly for ClO 2 manufacture (ER and SVP processes),
for synthesis of other ClO x compounds,
as oxidation agent in uranium extraction
(for U(IV) U(VI)) and as herbizide
- commercial use of KClO 3 : fireworks and matches
HBrO 3 /BrO 3 -: - formation: (1) 3 Br2 + 6 OH- BrO 3 - + 5 Br- + 3 H2 O

(industrial process)
(2) Electrolysis of NaBr without cell separation
NaBr + 3 H2 O NaBrO 3 + 3 H2
(technical process)
(3) Oxidation with chlorine
Br- + 3 Cl2 + 6 OH- BrO 3 - + 6 Cl- +3 H2 O
- acid stable up to 50 %, than decomposes to Br2 , O2 and H2 O
- high oxidation power of the acid and the salts
- used for redox titrations (colourless red-brown, in acids)
BrO 3 - + 5 Br- + 6 H+ 3 Br2 + 3 H2 O
-industrial application in flour treatment
and in hair-setting lotions
HIO 3 /IO 3 -: - formation: (1) electrochemical or chemical oxidation of I2

e.g. I2 + 6 H2 O + 5 Cl2 2 HIO 3 + 10 HCl
(2) MClO 3 + I2 Cl2 + 2 MIO 3
(in hot HNO3 , M = Na, K)
(3) 3 I2 + 6 OH- IO 3 - + 5 I- + 3 H2 O
(4) NaIO 3 + H2 SO4 HIO 3 + NaHSO4
- (1) and (2) are the commercial routes
- high stability of the acid and the salts
- high oxidation power of the acid,
moderate oxidation power of the salts
Perhalogenic acids (HOX4) and Their Salts (XO 4-)
HClO4/ClO4-: - formation: (1) Heating of alkali chlorates

4 MClO3 3 MClO4 + 2 MCl
(industrial process in case of M = Na,
metathesis reactions with NaClO4 to form
the other perchlorates)
(2) anodic oxidation of chlorates
in basic solutions (technical process)
ClO3- + H2 O ClO4- + 2 H++ 2 e -
(3) electrolysis of chlorine in perchloric acid
at 0 C (Merck process):
Cl2 + 8 H2O 2 ClO4- + 16 H+ + 14 e-
(4) NaClO4 + HCl HClO4 +NaCl
- stable even as poor substance, salts in general stable
- less oxidation power than chlorites, especially in case of
diluted acid
- low solubility of K, Rb and Cs salts
- acid is traded in concentrations of 60-62 % in H2O
- used in fireworks and as oxidation agent in rocket fuels
BrO4-: - formation: Oxidation of bromates with fluorine

BrO3- + F2 + H 2O BrO4- + 2 HF
- acid stable up to 55 %, pure salts are stable > 150 C
- less oxidation power because of kinetic hindering
- decomposition at high temperatures only to BrO3-
HIO4/IO4-: - formation: (1) Oxidation of iodates with chlorine

IO3- + Cl 2 + H2O IO4- + 2 HCl
(2) Thermal disproportionation of iodates
Ba(IO3)2 Ba5(IO6)2 + 4 I2 + 9 O2
- existence of periodate acid HIO4, H5 IO6 ortho-periodic
acid and H7 I3O14 tri-periodic acid
(in water solution only H5 IO6)
- anions in solutions: H4IO6-, H3 IO62-, H2IO63-, IO4-, H2 I2O104-
- anions in salts of HIO4, H3 IO5 (meso-acid), H5 IO6, H6I2 O10,
H4I2O9 (di-periodic acids), H7I3 O14

Lehrbuch der anorganischen Chemie,

Stoffsystematik,
(7) P.W. Atkins,

(8) Werner Bchner, Reinhard Schliebs, Gerhard Winter, Karl Heinz Bschel,
Industrial Inorganic Chemistry,
VCH Verlagsgesellschaft Weinheim, 1989
Pseudo Halogenes
Atom Groups
Atom group Hydrogen compound Anion
CN cyanic acid HCN cyanide CN-
N3 nitrogen hydrogen acid - HN3 azide N3-
cyan acid - HNCO

OCN isocyan acid - HOCN cyanate NCO-
fulminate OCN-
thiocyan acid HSCN
SCN isothicyan acid - HNCS thiocyanate NCS-
isothiocyanate SCN-
Similar properties like halogens (Cl, Br. I) with respect to

- acid reaction of hydrogen compounds
solubility in water
(high solubility of alkali salts,
low solubility of silver, mercury and lead salts)
- oxidation number = -1
- formation of singe bounded ligands in complexes
- dimerisation to molecules X2 reacting like halogen molecules
(e.g. (CN) 2, (NCS) 2)
- formation of interhalogen and inter- pseudohalogen compounds
(e.g. (NCS)Cl 3, (NC)(NCS))
- com- and disproportionation reactions
(e.g. (CN) 2 + 2 OH- CN- + OCN- + H2O)
Chapter 6
Chalkogens
(Oxygen Group)
Group Oxygen Sulphur Selenium Tellurium Polonium

Members (O) (S) (Se) (Te) (Po)
Rel. Atomic 15.999 32.06 78.96 127.60 [209.98]
Mass
Discovery 1772 discoverer 1818 1782 1898
Scheele, unknown Berzelius von M. Curie
1774 (known Reichen-
Pristley since stein
antiquity)
Percentage on 48.9 0.030 5 * 10-6 1 * 10-6 2 * 10-14
earth [Mass-%] (radio-
active)
melting point -218.75 119.6 220.5 449.5 254
[C]
boiling point -182.97 444.6 684.8 1390 962
[C]
state at room colourless, yellow non- red non- silver silver
temperature (25 odourless, metallic metallic metallic metallic
C) tasteless gas solid (S8 ) (Se 8 ) and solid solid
and 1 bar (O2 ) grey
metallic
(Se 8 ) solids
Electron 3.5 2.5 2.4 2.1 2.0
negativity
valence -2 -2+6 -2+6 -2+6 -2+6
numbers in
compounds
Reducing/
oxidising reducing
Oxidation
power power
Power
Metallic/ Non-
metallic non-metallic metallic
character
Acid/Basic
properties of acid base
oxides
Stability of
valence states
-2/-1
+2
+4
+6
Electron configuration: sp 4(d 10) need of accepting two electrons

or loosing 6 electrons for full saturation of electron
shells
General Properties of Chalkogenes (1)
Hydrogen compounds and metal salts (-ides)

- stability of hydrogen compounds decreases
H2O > H2S > H2Se >H2 Te > H2Po
- bonding energy H-X decreases (463 kJ/mol (H2O), 348 kJ/mol (H2S),
276 kJ/mol (H2Se), 239 kJ/mol (H2 Te))
- acid strength increases (pK s(25 C = 15.74 (H2O), 6.92 (H2S),
3.77 (H2Se), 2.64 (H2 Te))
2-
- anions X are stable in case of all VIa group elements
- formation of hydrogen per-compounds (H-X-X-H), per-anions (X22-) and
polyanions (Xn2-)
Halogen compounds (chalkogen halogenides)
- oxygen halogen compounds:

O2F, O2F2, Hal 2O, Hal 2O3, HalO2, Hal 2O5, HalO3, Hal 2O7 (Hal = Cl, Br, I)
- sulphur and higher elements:
formed in the compositions XnHal 2 (n = 2, 3, 4), XHal 2, XHal 4 and XHal 6 with X as
the electropositive partner
- compounds can be formed from the elements, by com- and disproportionation
reactions and by treatment of oxides with halogenating agents (H-Hal, M-Hal)
General Properties of Chalkogenes (2)
Oxides
XO X2 O3 XO2 X2 O5 XO3
oxidation +2 +3 +4 +5 +6
state
S SO2 SO3
colourless gas colourless
liquid
Se (SeO 2 )n Se2 O5 SeO 3
white needles, colourless
oxidising solid
agent
Te TeO 2 Te2 O5 TeO 3
yellow solid yellow solid
Po PoO black PoO2 PoO3
solid yellow-red only observed
solid in traces
Acids/Bases
+2: +4: H2 XO3 +6: H2 XO4 oxidation

H2 SO3 H2 SO4 power
pKs1/2 = 1.81/6.99, pKs1/2 = -3/1.89,
moderate reducing moderate oxidation
power power
H2 SeO 3 H2 SeO 4
strong acid strong acid
pKs1/2 = 2.62/8.3 pKs2 = 1.74
- H2 TeO 3 o-H6 TeO 6
amphoteric pKs1/2 = 7.7/10.95,
pKs1/2 = 2.48/7.7, high oxidation
pKB1 = 2.7, power
low stability
Po(OH)2 - basic H2 PoO3 - amphoteric -
acid strenght
Oxygen
Natural sources
- elementary: main component of air (20.5 %)
- in compounds: water (88 %),
oxides and oxygen containing salts (e.g. SO42-, CO32-),
essential part of biosphere
Manufacturing
- in industry: air rectification (Linde process),
electrolysis of water
- in laboratory: thermal or catalytic decomposition of peroxides
Oxygen species
- neutral molecules: O2, O3 (ozone)
2-
- negative charged species: O (oxides - colourless),
O22- (peroxides - colourless),
O2- (hyperoxides - yellow),
O3- (ozonides - red)
- positive charged species: O2+ (dioxygenyl) in O2PtF6
Properties of O2
- colourless, tasteless and odourless gas
- low solubility in water (3.05 l /100 l H2O)
- essential for life (in dilution, toxic after long time exposure in elementary form)
- high reactivity with near all elements, but only at high temperature or after catalytic
or photochemical activation, mostly strong exothermic reactions
- reactivity is increased by adding small amounts of humidity
Application of O2
- generation of high temperatures (metallurgy, welding)
- coal gasification
- TiO2 production from TiCl 4
- medicine
- fuel cells
Ozone
Natural sources
- traces in atmosphere
Manufacturing
- 3 O2 + 285.6 kJ/mol 2 O3
- in industry/laboratory: activation of oxygen with
- thermal energy (>3500 K, very poor yields),
- electrical energy
O3
(dark discharges ozonisator by SIEMENS),
- photochemical energy ( < 242 nm) or
- chemical energy
(e.g. oxidation of white phosphor)
- electrolysis of water, H2O2, HMnO4
- F2 + H2 O 2 HF + O, O + O2 O3
ozonisator by SIEMENS
water cooling
O2
Properties
- blue gas with characteristic odour
- melting point: -192.5 C, boiling point: -110.5 C
- well soluble in water (49.4 l/100 l H2O)
- high endothermic, meta-stable compound
- high oxidation power (O3 O2 + O)
Application
- air disinfections
- water disinfections
- sterilisation of food
Ozone in the Troposphere (Bad Ozone)
Troposphere = lowest atmospheric layer up to 10 km height
Natural equilibrium between nitrogen oxides and ozone
Photochemical smog = anthropogenic increase

- of NOx concentration
- of hydrocarbon and CO concentration
Hydrocarbons, oxygenates and CO form peroxo radicals,

which oxidise NO to NO2 instead of O3 (reaction 3)
UV radiation
emissions
hydrocarbons, CO
emissions
Ozone in the Stratosphere (Good Ozone)

Stratosphere = atmospheric layer between 10 and 50 km height
Chapman cycle
- ozone formation: O2 + h (< 242 nm) +

O + O2 + M (inert molecule) 3
- ozone decomposition: O3 + h (< 1200 nm) 2 +
O3 + O 2 2
Catalytic ozone decomposition
O3 + X O2 + OX
OX+ O X + O2
O3 + O X
2 2
(X = NO, H, OH natural, Cl, Br anthropogenic)
Peroxides
Industrial production of H2O2

- water dehydrogenation: electrolysis of sulphuric acid
2 H2SO4 H2S2O8 + H2 (electrolysis),
H2S2O8 +2 H2 O 2 H2O2 + 2 H2 SO4
- oxygen hydrogenation:
(I) 2 step antrachinone process (BASF)
(II) 1 step isopropanol process (Shell)

isopropanol + O2 H2O2 +acetone
Properties of H2O2
- meta-stable compound
- decomposition: 2 H2O2 2 H2O + O2 + 196.2 kJ/mol
catalysed by noble metals, MnO2, high surface area particles,
inhibited by acids as H3PO4 and organic acids
DO NOT STORE H2O2 IN GLASS BOTTLES !!!
- wide application as a clean oxidation agent

- reducing properties with strong oxidation agents (e.g. Ag2 O Ag)
Technical application of H2 O2
- leaching agent
- production of perborates for detergents: NaBO2 + H2O2 NaBO3 + H2 O
Alkali metal peroxides

- Na2O2: production by 2 step oxidation of Na,
strong oxidation agent, use in paper and textile leaching,
use in respirators for CO2 removal
Na2O2 + CO2 Na2 CO3 + 0.5 O2
- BaO2: production by thermal oxidation of BaO at 500-600 C
2 BaO + O2 2 BaO2,
use as igniting agent
The Ozone Leak in Antarctica (1)
1957 begin of ozone measurements in Halley Bay
300
250
200
150
100
50
0
1960- 1984 1985 1986 1987
1970
1974 Montreal protocol

= end of the use of fully halogenated hydrocarbons
1985 discovery of the ozone leak
2002 Stop of increasing ozone leak
Photos: Magdeburger Volksstimme, Oct 12th 2002

The Ozone Leak in Antarctica (2)
(1) Formation of reservoir substances
- formation occurs in warmer areas

- migration of the precursors to Antarctica
(2) Antarctic winter (-75-85 C)
- decomposition of reservoir substances in polar stratospheric clouds (PSC) by

catalytic reaction with ice and HNO3 3 H2O crystals
- formation of active chlorine
(3) Begin of the sunshine period (end of September)
(4) Antarctic spring
- warming of the atmosphere, changing of air pressure

- mixing and replacing of Antarctic stratospheric air
- chlorine content decreases, relaxation of the ozone layer
Sulphur (1)
Natural sources
- in elementary form in sediments
(Italy, Poland, USA, Mexico, Peru, Chile, Japan)
- in reduced form in sulphidic ores
(FeS2 pyrit, CuFeS2, FeAsS, PbS, Cu2S, MoS2, ZnS, HgS, AsSx)
- in oxidised form
(CaSO4 2 H2 O gypsum, CaSO4 anhydrite, MgSO4 7 H2O,
MgSO4 H2 O, BaSO4, SrSO4, Na2 SO4 10 H2O)
Industrial production of elementary sulphur

- Mining
- Extraction with superheated water and air under high pressure
(Frasch process)
pressured
sulphur air steam
steam
sulphur containing
limestone
molten
sulphur
rock
- calcination of pyrite at 1200 C under absence of air

(Outokumpu process)
83 kJ/mol + FeS2 FeS + S
- Claus process
use of H2S from desulphuration of natural gas, petrol, oil,
synthesis gas or coke oven gas,
2 step process
(1) H2S + 1.5 O2 SO2 + H2O
(non-catalytic combustion)
(2) 2 H2S + SO2 3 S + 2 H2O
(220-300 C, alumina supported CoMo oxide catalyst,
reactor cascade)
- COPE process = modified Claus process with partial reaction gas recycle
Application of sulphur (50 * 106 t/a)

- Production of sulphur oxides/sulphuric acid (85-90 %), CS2 and P 2S5
- vulcanisation of rubber
- pharmaceuticals, exterminators
- concrete and road building, paints
- gunpowder and fireworks
Sulphur (2)
Sulphur modifications
melting boiling
point point
solid, solid, 119 C 159 C gaseous

light near liquid, red blue violet
yellow colourless light yellow,
low viscosity
159 C - 243 C
Chain length in solid and liquid state:
liquid,
dark red-brown, -S and -S S8 molecules
high viscosity
-S S8 molecules
243 C 445 C -S Sn molecules (n = 530)
liquid, -S polymerised molecules
dark red-brown,
low viscosity
Chemical properties
- reacts exothermally with most elements (without Au, Pt, Ir, N2, Te, I2 and noble
gases) at moderate temperatures
- higher reactivity than oxygen
- reacts with oxidising acids (to H2SO4) and alkaline solutions (forming
polysulphides - Sn2- - and thiosulphates S2O32-)
- inert in non-oxidising acids and in water
- oxidation number of 2 in sulphides (S2-) formed with electropositive elements
- oxidation number of +2, +4 and +6 in compounds with electronegative elements
(oxygen, halogens)
Sulphides
Hydrogen sulphide H2 S
- natural sources: occurs in crude oil and natural gas,
emitted from volcanos and mineral springs,
biological decomposition of sulphur containing
organic compounds
- synthesis: a) from the elements H2 + S H2S + 20.6 kJ/mol
at 600 C, MoS2 or alumina supported Co/MoOx
catalysts (industrial process)
b) treating of sulphides (e.g. pyrite)
with hydrochloric acid
FeS + 2 HCl FeCl 2 + H2S
(laboratory method, using Kipps apparatus)
c) obtained from purification of crude oil, natural gas
and synthesis gas
- properties: stinking, colourless, high toxic gas, soluble in water,
melting point: -85.6 C, boiling point: -60.3 C
weak acid H2S H+ + HS- 2 H+ + S2-,
moderate reducing agent
- existence of hydrogen polysulphides H2Sn, and their metal salts
Industrial important metal sulphides

- Na2 S, NaHS: prodced from Na2 SO4 + C or
from sodium polysulphide + Na amalgam,
synthesis of organic sulphur compounds,
depilatory in leather industry, ore flotation,
precipitation of heavy metal ions
- K2S, NH4HS
Sulphur Oxides (1)
- existence of mono-sulphur oxides (SO, SO2, SO3 and SO4 oxidation number +6)
and poly-sulphur oxides (Sn O, SnO2, S2O2, S3O9, (SO3-4)n)
- industrial relevance of SO2 and SO3
- SO2 and SO3 are anthropogenic emitted precursors of acid rain
Sulphur dioxide SO2
- Synthesis: (I) single or two stage combustion of elementary sulphur

in air or pure O2
S + O2 SO2 + 297 kJ/mol
(II) calcination of sulphide ores (e.g. pyrite) in air or O2
using multiple hearth reactors, rotary kilns
or fluidised bed reactors (650-1100 C)
2 FeS2 + 5.5 O2 Fe2O3 + 4 SO2 + 1655 kJ/mol,
additional process step for removal of dust and catalyst
poisons with respect to SO2 to SO3 oxidation
(III) purification and evaporation of diluted waste acids
(e.g. Venturi reconcentartion process, submerged-
burner process, Pauling-Plinke process,
Bayer-Bertrams process), yielding to 96 % acid
(IV) SO2 extraction from wastes of exhaust air cleaning
a) Mller-Khne process (producing of cement)
4 CaSO4 + 4 SiO2 +2 C
4 CaO SiO2+ 4 SO2 + 2 CO2 (1400 C)
b) re-use of FeSO4 wastes from TiO2 manufacture
(Bayer)
601 kJ/mol + FeSO4
Fe2O3 + 2 SO2 + 0.5 O2 + H2O (900 C)
- Properties: sticking odorous, colourless toxic gas, soluble in water
(weak acid reaction),
melting point: -75.5 C, boiling point: -10.0 C,
reducing agent (forming SO3),
main component of acid smog in winters
- Use: Production of sulphuric acid and sulphur containing
chemicals (e.g. sulphites, dithionited, thiosulphates),
disinfections agent (beer and wine industry),
leaching agent
Sulphur Oxides (2)
Sulphur trioxide SO3
- Synthesis: (I) three stage catalytic oxidation of SO2 with air

(contact process)
2 SO2 + O2 2 SO3 + 99 kJ/mol
at 410-440 C, catalyst: kieselgur supported V2 O5
(V2O5 + SO2 V2 O4 + SO3, V2O4 + 0.5 O2 V2O5)
multi-stage fixed bed reactors
1 1st tray
SO3 decomposition catalyst (60 % conversion)
1st heat
exchanger
2nd tray
catalyst (90 % conversion)
SO3 yield
SO3 formation 2nd heat

exchanger
3rd tray
catalyst (95 % conversion)
3rd heat
exchanger
4th tray
catalyst
temperature [C] (98 % conversion)
final step:
sequential adsorption of SO3
and water in conc. H2SO4
(II) Nitrous process (lead chamber or tower process)
at 80 C, use of gaseous NO2 as the catalyst
(N2O3 + SO2 2 NO + SO3, 2 NO + 0.5 O2 N2O3)
advantages: operates with lean reactant gas
(0.5-3 % SO2),
low operation temperature
disadvantage: low final H2SO4 concentration
(78 %)
(III) Sulphur recycling from SOx containing wastes
- Properties: 3 modifications -SO3 (= (SO3)p), -SO3 (= (SO3)n),
-SO3 (= (SO3)3) p > n > 3
melting points: -SO3 62.2 C, -SO3 32.5 C, -SO3 16.9 C
(depolymerisation of -SO3 and -SO3 during melting)
boiling point: -SO3 44.4 C,
colourless, soluble in water, forming H2SO4
(strong acid reaction),
oxidising agent (forming SO2),
- Application: production of H2SO4 and other sulphur compounds,
production of alkyl sulphates (detergents)
Acids of Sulphur Oxides
Types of sulphate anions
sulphoxylate sulphite sulphate peroxo sulphate
thiosulphate dithionite disulphite dithionate disulphate peroxo disulphate
- acids stable at high concentrations:

sulphuric acid H2SO4, , disulphuric acid H2S2O7,
peroxo sulphuric acid H2SO5, peroxo disulphuric acid H2S2O8,
thiosulphuric acid H2S2O3
- other acids are stable only in dilution or as salts
- general synthesis routes
reduction: 2 SO2 + 2 e - S2O42-, 2 SO3 + 2 e - S2 O62-
condensation: 2 HSO3- S2O62- + H2O,
2 HSO4- S2O72- + H2O
oxidation: 2 SO32- S2O62- + 2 e -, 2 SO42- S2 O82- + 2 e -
- economically important acids:
sulphurous acid H2 SO3, sulphuric acid H2 SO4
Sulphurous and Sulphuric Acid
Sulphurous acid H2SO3

Manufacture: SO2 + H2O [H2 SO3 ] H+ + HSO3 -
(K < 10-9 )
Properties: acid is stable only in dilution, salts are stable,
moderate acid (K S1 = 1.54 10-2 , KS2 = 1.02 10-9 )
reducing agent (forming H2 SO4 / SO42-),
can be oxidised by strong reducing agents
e.g. 6 H+ + 6 e- + SO2 H2 S + 2 H2O (Zn/HCl),
2 SO2 + 4 H+ + 4 e- S + 2 H2O (Fe2+),
2 SO2 + 2 H+ + 4 e- S2 O32- + H2O (HCOO-, S),
Sulphuric acid H2 SO4

Manufacture: contact process (see SO3 )
carried out in industry as a process unit
outgoing from S, H2 S or sulphidic ores
(I) Oxidation of the starting material to SO2
(II) Oxidation of SO2 to SO3
(III) Formation of sulphuric acid in conc. H2 SO4
SO3 + H2 SO4 H2 S2 O7
H2 S2 O7 + H2 O 2 H2 SO4
Properties: very strong, oxidising acid
(K S1 = 103 , KS2 = 1.3 10-2 ),
high affinity to water, strong heat accumulation
during dilution,
melting point: 3.0 C (98 % acid),
boiling point: 279.6 C (100 % acid),
azeotrope with water (98/2) boiling at 338 C,
strong etching and oxidation agent, oxidises under SO2 formation
organic substances to elementary carbon (coke), metals (without Pt
and Au) to salts, hydrogen compounds to elements (HI I2 , H2 S
S)
weak reducing agent (forming peroxo disulphuric acid)
oleum = solution of SO3 in H2 SO4
Application: one of the most important base chemicals,
production of fertilisers, mineral acids,
inorganic and organic sulphates (e.g. detergents),
uses as a catalyst (water removal),
as electrolyte in batteries, as drying agent
Salts from Acids of Sulphur Oxides
Sodium hydrogen sulphite NaHSO3

Manufacture: NaOH+ SO2 NaHSO3
Application: bleaching agent
Sodium disulphite Na2 S2O5

Manufacture: reacting NaOH + SO2 in a saturated NaHSO3 solution
Application: photographic industry, paper industry, textile industry,
food industry, water treatment
Sodium disulphite Na2 SO3

Manufacture: reacting NaOH + SO2 in a saturated Na2 SO3 solution
Application: photographic industry, paper industry, textile industry,
food industry, water treatment
Calcium hydrogen sulphite Na2 S2O5

Manufacture: reacting limestone + SO2
Application: production of sulphite cellulose
Sodium thiosulphate Na2S2O3 and ammonium thiosulphate (NH4)S2O3

Manufacture: (I) 2 NaOH + SO2 + S Na2 S2O3 + H2 O;
Na2 SO3 + S Na2S2O3 (50-100 C)
(II) 2 Na2 S + Na2 CO3 + 4 SO2 3 Na2 S2 O3 +CO2
(III) 2 NH3 + SO2 + H2 O (NH4 )2 SO3 ,
(NH4 )2 SO3 + S (NH4 )2 S2O3 (80-110 C)
Application: fixing salts in photography (formation of [Ag(S2 O3 )]-
and [Ag(S2 O3 )2 ]3- complexes soluble in H2 O),
anti-chlorination agent in bleaching plants
and paper industry (Cl2 Cl-),
flue gas desulphurisation
Sodium dithionate Na2 S2O4

Manufacture: (I) Zinc dust process (40 C)
Zn + 2 SO2 ZnS2 O4,
Zn2 S2O4 +2 NaOH Zn(OH) 2 +Na2 S2O4
(II) Formate process
(HCOO) - + OH- +2 SO2 S2O42- +CO2 + H2O
(III) Amalgam process
(IV) Sodium tetrahydroborate process
Application: reducing agent in textile dying and printing
starting material for sodium hydroxymethansulphinate
(HO-CH2-SO2Na) used in direct and discharged
printing
Other Important Sulphur Containing Compounds (1)
Disulphur dichloride S2Cl2

Manufacture: 2 S + Cl2 S2 Cl2 at 240 C, catalysts: FeCl3 or AlCl3
Application: starting material for SOCl2 production,
reaction with polyols gives additives
for high pressure lubricating oils,
catalyst for chlorination of acetic acid,
vulcanisation of rubber
Sulphur dichloride SCl 2

Manufacture: S2 Cl2 + Cl2 2 SCl2 at low temperatures, catalyst: I2
Application: starting material for SOCl2 production,
sulphidising and chlorination reactions
Thionyl chloride SOCl 2

Manufacture: (I) reaction of SO2 or SO3 with Cl2 , SCl2 and S2 Cl2
over an activated carbon catalyst
(II) SO2Cl2 + PCl3 SOCl2 + POCl3

Application: chlorination agent in organic chemistry
(producing of herbicides, pesticides, pharmaceuticals,
dyes and pigments),
non-aqueous electrolyte in galvanic cells
Sulphuryl chloride SO2Cl2

Manufacture: SO2 + Cl2 SO2 Cl2 , catalyst: activated carbon
Application: chlorination and sulphochlorination agent
(producing of herbicides, pesticides, pharmaceuticals,
dyes and pigments)
Other Important Sulphur Containing Compounds (2)
Chlorosulphonic acid HSO3Cl

Manufacture: SO3 + HCl HSO3 Cl in HSO3 Cl
Application: mild sulphonating and chlorosulphonating agent
in organic chemistry
Fluorosulphonic acid HSO3F

Manufacture: SO3 + HF HSO3 F in HSO3 F
Application: fluorination agent in inorganic and organic chemistry
(synthesis of sulphofluorides and sulphonic acids),
catalyst for alkylation and polymerisation reactions,
polishing agent for lead crystal glass
Carbon disulphide CS2

Manufacture: (I) C + S2 CS2 at 720-750 C
(II) CH4 + 2 S2 CS2 + 2 H2S at 650-750 C
Application: viscose industry (rayon), cellophan production,
synthesis of CCl4 ,
production of vulcanisation accelerators,
flotation agents, corrosion inhibitors, herbicides and
pharmaceuticals
Selenium and Tellurium
Selenium
Manufacturing: 1. Oxidation of anode sludge from Cu electrolysis
Ag2 Se + O2 + Na2 CO3
Na2 SeO 3 + 2 Ag + CO2
2. Acidification with H2 SO4
( separation of SeO 3 2- and non-soluble TeO 2 )
3. Reduction of with SO2
H2 SeO 3 + 2 SO 2 + H2O Se + 2 H2 SO4
Properties: 2 modifications in solid state
- non- metallic red selenium Se8
- semimetallic grey selenium Se8
Application: electronics (e.g. rectifier and photo cells,
photocopiers
Tellurium
Manufacturing: 1. Oxidation of anode sludge from Cu electrolysis
Ag2 Te + O2 + Na2CO3
Na2 TeO 3 + 2 Ag + CO2
2. Acidification with H2 SO4
( precipitation of TeO 2 )
3. Resolving of TeO 2 in base solutions
4. Chemical reduction of with SO2
TeO 3 2- + 2 SO 2 + H2 O Te + 2 SO42-
or electrochemical reduction
Properties: silver-white colour with metallic brilliance,
semiconductor
Application: additive in alloys of steel, copper, lead and tin
(increase of mechanical properties)
Water
- covers 71 % of earths surface

- 97 % of water is located in the oceans
- essential part of plants (until 95 %) and animals (human: > 50 %)
water molecule
- protons possess positive charge

- electrons possess negative charge
dipole momentum
104.9
Physical properties
- increasing volume during freezing

( water = 0.9999 g/cm, ice = 0.9168 g/cm)
- maximum de nsity at 3.98 C (1.0000 g/cm)
- strong intramolecular hydrogen bridging bonds
(high melting and boiling temperature)
p-T diagram chlarathe structure of ice
liquid water
pressure
ice
water vapour
temperature
Chemical properties
- solves primarily ionic salts (dissociation of salts and solvatisation of the ions) and
polar organic compounds (methanol, ethanol)
- autoprotolysis reaction 2 H2O H3O+ + OH- (K = 10-14)
- high thermal stability, low reactivity
- acts normally as an moderate oxidation agent, with fluorine and other strong
oxidation agents as a reducing agent
Chapter 7
Pnictogens
(Nitrogen Group)
Group Nitrogen Phosphorus Arsenic Antimony Bismuth

Members (N) (P) (As) (Sb) (Bi)
Rel. Atomic 14.007 30.97 74.92 121.75 208.98
Mass
Discovery 1772 1669 ca. 1250 1492 known since
Scheele Brand Magnus Valentin antique
Percentage on 0.017 0.10 1.7 * 10-4 2 * 10-5 2 * 10-5
earth
[Mass-%]
melting point -209.99 44.25 (P 4 ) - 630.7 271.3
[C]
boiling point -195.82 280.5 (P 4 ) 616 1635 1580
[C] (subli-
mation)
state at room colourless, white non- yellow non-
temperature (25 odourless, metallic metallic
C) tasteless gas solid (P 4 ), solid (As4 ),
and 1 bar red non- black non-
metallic metallic
solid (P 8 ), solid (As8 ),
black semi- grey grey silver
metallic metallic metallic metallic
solid (P 8 ), solid (As8 ), solid (Sb8 ) solid (Bi8 )
purple non-
metallic
solid (P 8 )
Electron 3.0 2.1 2.0 1.9 1.9
negativity
valence -3+5 -3+5 -3+5 -3+5 +3 (+5)
numbers in
compounds
Reducing/
oxidising reducing
Oxidation
power power
Power
Metallic/ Non-
metallic non-metallic metallic
character
Acid/Basic
properties of acid base
oxides
Stability of
valence states
3
+3
+5
Electron configuration: sp3 (d10 ) need of accepting 3 electrons or loosing

5 electrons for full saturation of electron shells
General Properties of Pnictogens (1)
Valency states:
- - 3 with electropositive elements (stability decreases with increasing period number,

-3 is unknown for Bi)
- + 3 and + 5 (+5 is favoured at lower, + 3 at higher period numbers)

NH3 ( B H = 46 kJ/mol) > PH3 (- 5 kJ/mol) > AsH3 (+ 66 kJ/mol)
> SbH3 (+ 145 kJ/mol) > BiH3 (+ 278 kJ/mol)
- bonding energy H-X decreases
NH3 (391 kJ/mol) < PH3 (227 kJ/mol) > AsH3 (297 kJ/mol)
> SbH3 (257 kJ/mol) > BiH3 (194 kJ/mol)
- basic strength decreases
(NH3 (pKB(25 C) = 4.75) < PH3 (27),
AsH3, SbH3 and BiH3 are not stable in aqueous solutions)
- N and P form a wide variety of compounds with more than one pnictogen atom (e.g.
N2H4, P 3H5)
Halogen compounds (pnictogen halogenides)
- nitrogen: formed in the compositions NX3, N2X4, N2X2 and N3X as derivates from
the hydrogen compound
- higher elements: XHal 3, X2Hal 4 and XHal 5 with X as the electropositive partner
- formation of oxyhalogenides (e.g. NOCl, POCl 3)
General Properties of Pnictogens (2)
Oxygen compounds (pnictogen oxides)
- nitrogen: formed in the compositions N2O, NO, N2 O2, N2 O3, NO2, N2O4, N2O5, NO3
and N2O6
- higher elements: X2O3 and X2O5 with X as the electropositive partner
Acids/Bases
- nitrogen: H3 NO, HNO, H2N2O2, H2N2O3, HNO2, HNO3, NO43- and HNO4
- phosphorus: H3PO2, H4P 2O4, H3PO3, H2P 4O5, H2P 4O6, H3PO4, H4P 2O7 H4P 2O8 and
H3PO5
- higher elements: H3XO3 and H3XO4
- acidity decreases with increasing period number, acids containing X(V) are stronger
than acids with X(III)
- N, P, As and Sb oxides form acids, Bi 2O3 possess basic properties
Sulphur compounds (pnictogen sulphides)
- nitrogen: sulphur nitrides (e.g. S4N4), sulphur nitride halogenides

(e.g. (NSX) n), sulphur nitride oxides (e.g. (NSXO) 3) and sulphuric acid derivates of
hydrogen compounds (e.g. NH2 SO3H amido sulphuric acid)
- phosphorus: X4Sn (P: n = 2-10, As: n = 3-10, similar composition for selenids)
- higher elements: X2S3 and X2S5, for As, Sb and Bi with metal sulphide character
Nitrogen
Natural sources
- elementary: main component of air (79.5 %)
- in compounds: water (solved nitrate salts 1 % of total N),
salt deposits (Chile, India)
essential part of biosphere (amino acids) -
0.001 % of total N
Manufacturing
- in industry: air rectification (Linde process),
- in laboratory: thermal or catalytic remo val of oxygen from air
(product contains noble gases), pure nitrogen by
oxidation of ammonia (NH3 + HNO2 N2 + 2 H2O)
Nitrogen species
- N2, N3- (nitride), N3- (azide)
Properties
- colourless, tasteless and odourless gas
- triple bond between the nitrogen atoms
- low solubility in water (3.05 l /100 l H2O)
- essential for life (formation of amino acids, assimilation for most plants as NH4+,
NO2-, NO3- and urea, special bacteria azobacter - can convert gaseous N2)
- very poor reactivity with near all elements, only at high temperature, mostly strong
endothermic or kinetically hindered reactions
Application of N2
- inert purging gas
- cooling agent (in liquid state)
- synthesis of ammonia, hydrazine, hydoxylamine and nitric acid
Important Nitrogen Hydrogen Compounds (1)
Ammonia NH3
- Manufacturing
from the elements: N2 + 3 H2 2 NH3
- Properties
colourless toxic gas with sticking odour,
melting point: -77.8 C, boiling point: -33.4 C,
high solubility in water (702l/l H2O at 20 C),
forming weak basic solutions (NH3 + H2O NH4 + + OH-,
pK B = 4.75)
- Application
production of fertilizers (80 %, incl. fertilizers from nitric acid),
plastics (10 %), explosives (5 %), herbicides, organic chemicals
one of the most important industrial chemicals
Hydrazine H2NNH2
- Manufacturing
(1) oxidation of ammonia with hypochlorites (in-situ formation
from Cl 2): 2 NH3 + ClO- N2H4 + H 2O + Cl -
(2 step Raschig process in base solution,
2 step Bayer process in acetone)
(2) oxidation of ammonia with H2O2 and methyl ethyl ketone
(2 step Pechiney Ugine Kulmann process)
(3) 2 step oxidation of urea with hypochlorites
presently not in commercial use
- Properties
colourless, fuming liquid with high viscosity and strange odour,
melting point: 2.0 C, boiling point: 113.5 C,
forming a hydrate N2H4 H2 O (high viscose liquid with fishlike
odour, melting point: - 51.7 C, boiling point: 118.5 C),
endothermic meta-stable compound, decomposition only at
high temperatures,
soluble in water with basic reaction ((H3N-NH2)+ +OH-
- Application
synthesis of a large amount of organic chemicals,
of polymerisation initiator, of herbicides and of pharmaceuticals;
acts in water as a corrosion inhibitor
Important Nitrogen Hydrogen Compounds (2)
Hydroxylamine NH2OH
- Manufacturing
(1) modified Raschig process (3 step process)
HNO2 + 2 H2 SO3 + H2O NH2OH + 2 H2 SO4,
carried out with NH4NO2 and SO2 in diluted H2 SO4
(2) NO reduction process (BASF, Iventa favoured process)
2 NO + 3 H2 2 NH2OH (in H2SO4, catalyst: Pt or Pd on C)
(3) Nitrate reduction process (3 step process using NH4NO3,
hydrogen, phosphoric acid and cyclohexanone)
- Properties
colourless, odourless solid (needles), melting point: 33 C,
decomposes at moderate temperatures to NH3, N2 and H2 O,
stable only in the absence of air or in aqueous solutions,
weak basic properties (pKB = 8.2), salts (e.g. sulphates)
posses much higher stability
- Application
production of caprolactam (97 %) for synthetic textiles,
of pharmaceuticals, herbicides and l acquers, anti-oxidising agent
Nitrogen hydrogen acid HN3

- Manufacturing
(1) from amides (obtained by the reaction of alkali metals with
ammonia: 2 Na + 2 NH3 2 NaNH2 + H 2) and dinitrogen
monoxide: NaNH2 + N2 O NaN3 + H2O (190 C)
(2) from amides and nitrates:
3 NaNH2 +NaNO3 NaN3 + 3 NaOH + NH3
(100 C, high pressure, in liquid NH3)
(3) from salpeterous acid and hydrazine:
HNO2 + N2H4 HN3 + 2 H2O (0 C, in ether)
90 % acid can be obtained by distillation with diluted H2 SO4
and water removal with CaCl 2
- Properties
colourless, low viscose and high toxic liquid
with piercing, unbearable odour,
melting point: - 80 C, boiling point: 35.7 C,
strong endothermic meta-stable compound,
explosion at high temperatures and after blow
(decomposition to the elements)
soluble in water with weak acid reaction (H3O+ +N3-, pK S = 4.92)
forms salts with properties similar to chlorides
- Application
Pb(N3)2 - made from Pb(NO3)2 and NaN3 -
is used in explosives and in air bags (cars).
Industrial Ammonia Synthesis
1. A Synthesis of High Complexity
Starting materials
- air (nitrogen and oxygen)
- water
- natural gas, oil or coke
Process scheme of an integrated ammonia plant
air natural gas heavy oil water coal
steam partial
rectification gasification
reforming oxidation
nitrogen oxygen
rough synthesis gas (N2, O2, CO, H2, H2S)
absorption of CO and H 2S
adsorption of CO2 and H2O on zeolithes
scrubbing with liquid N2 at 196 C and 80 bar
final synthesis gas (N2, H2)
ammonia synthesis
separation and purification of ammonia
final product (NH3)

2. Pre-Processing Steps (1)
Steam reforming
- raw materials: natural gas, naphta, water
- 2 C2H2n+2 + n H2O n CO + 2(n+1) H2
- Process steps:
(1) Desulphurisation of raw materials by hydrogenation
over CoO or NiO/MoO3 catalysts at 350 450 C
(2) Adsorption of formed H2S on ZnO
H2S + ZnO ZnS + H2O
(3) Primary reforming with steam at 700 830 C and 40 bars
over NiO/Al 2O3 catalysts
(4) Secondary reforming of methane at 1000 1200 C
CH4 + H2O CO + 3 H2
(5) Adjustment of stochiometric N/H ratio by feeding air
into the second reformer
Partial Oxidation
- raw materials: heavy fuel oil, air (enriched with oxygen)
- 2 C2H2n+2 + n O2 2n CO + 2(n+1) H2
- non-catalytical process at 1200 1500 C and 30 40 bar
- advantage: no desulphurisation step,
disadvantage: need of additional O2 (= additional air rectification step)
Coal gasification
- raw materials: coal, air, water
- C + H2O CO + H2, 2 C + O2 2 CO,
C + O2 CO2 for heat generation (1/3 of all coal is oxidised totally)
- 1200 C/solid-bed reactor (Lurgi process) or
800 1100 C/fluidised bed (Winckler process) or
1400 1600 C and 1 bar/fly ash (Koppers Totzeck process)
2. Pre-Processing Steps (2)
Conversion of carbon monoxides (~ 7 % in the feed)

- CO poisons ammonia synthesis catalyst
- CO + H2O CO2 + H2
- 350 - 380 C/FeCrO x catalyst (rest: 1 g CO /m air)
350 - 380 C/sulphur insensitive Co/Mo oxide catalyst (rest: 0.3 % CO)
Removal of CO and H2 S
- absorption with organic solvents (Rectisol process)
- absorption with K2CO3 (Benfield process)
- combination of both process modifications
Final purification
- aim: remove of any oxygen containing compounds (CO, CO2, H2O, O2) and of H2S
- adsorption of CO2 and H2O on zeolithes
- scrubbing with liquid N2 at 196 C and 80 bar (condensing of hydrocarbons, enrichment
of N2 if necessarily)
Final composition of synthesis gas

- H2 : 74.0 %, N2 : 24.7 % (H2 /N 2 = 3),
CH4 : 1.0 % Ar: 0.3 %, CO + CO2 < 10 ppm
Catalyst composition and preparation

- promoted -iron catalyst
- composition of starting mixture:
94.3 % Fe3 O4 , 0.8 % K2O, 2.3 % Al2 O3 , 1.7 % CaO, 0.5 % MgO,
0.4 % SiO 2
- preparation: (1) melting a mixture of magnetite (Fe3 O4 ) and
additives at 1600 2000 C
(2) rapid cooling
(3) crushing and sieving
(required particle diameter: 6-10 mm)
(4) in-situ reduction in the reactor with
synthesis gas at 350 400 C and 70 300 bar
(Fe3 O4 + 4 H2 3 Fe + 4 H2 O)
- Fe - active component
- K2O acts as electronic promoter (increase of activity)
- Al2 O3 and SiO 2 prevent sintering and provide acid/base sites
- CaO increase resistance against S and Cl
- other additives: oxides of Li, Be, V and U
- lifetime > 10 years
3. Synthesis and Purification of Ammonia
equilibrium limited, exothermic reaction with volume decrease
Equilibrium tubular reactor multiple-bed reactor

diagram with integrated with integrated
heat exchanger heat exchanger
pressure
resistent
outer tube
catalytic
contact
heat
exchanger
tube
temperature tubular reactor multiple-bed reactor
Process conditions
process country pressure [bar] temperature [C]
Haber Bosch process Germany 200 500

Casale process Italy 600-800 500
Fauser process Italy 200-300 500
Claude process France 900-1000 500-600
Mont Cenis process Germany 100 400-450
Kellog process USA 160-240 500
Product separation and purification

- obtained yield: 10-15 %
- product separation by freezing out the ammonia (-25 C)
and re-vaporisation or by absorption in water
- recycle of the unconverted reactants after removal of water
- compression and cooling for storage
Nitrogen Oxides and Acids
Overview
Oxdiation number of N +1 +2 +3 +4 +5
Oxides N2O NO, N2O3 NO2, N2O5
N2O2 N2O4
Acids HNO, N2O32- HNO2 HNO3 HNO4
H2N2O2 NO43-
Oxides:
- endothermic meta-stable compounds (without N2O4 and N2O5)
- occur during high temperature combustion processes from nitrogen oxidation
(instead of N2O)
- equilibriums NO/N2 O2 and NO2/N2O4 (dimerisation primarily at higher
temperatures)
- N2O, NO/N2O2 and NO2/N2 O4 have a large technical importance and environmental
relevance as anthropogenic emissions
( ozone and as precursors for acid rain)
Acids:
- acid strength increases with increasing number of oxygen atoms
- HNO2 (only stable in gas phase or in aqueous dilution salts are stable) and HNO3
are stable and of large technical importance
- H2N2O2 decomposes at room temperature within days, salts are stable
- HNO and HNO4 are meta-stable at low temperatures and decompose under normal
conditions
- N2O32- and NO43- exist only as salts
Nitrogen Oxides
Dinitrogen monoxide N2O (NNO)

- Industrial manufacturing
careful heating of ammo nium nitrate or
or of a mixture of NH3 and HNO3
or of a mixture of sodium nitrate and ammonium sulphate
(forming NH4NO3) at 200 C (danger of explosions!)
NH4NO3 N2O + 2 H2O + 124.1 kJ/mol,
product of biological nitrification and denitrification processes
- Properties
colourless gas with weak sweet odour and intoxicating effect,
melting point: - 90.9 C, boiling point: - 88.5 C,
well soluble in water (0.60 l/l H2O) and fats,
oxidation agent, supports combustion processes similar to oxygen
- Application
narcotic agent, propellant in ice-cream and whipped cream
Nitrogen monoxide NO
- formed by nitrogen oxidation at temperatures > 1500 C or
by Pt catalysed short contact time combustion of ammonia
(Ostwald process: 4 NH3 +5 O2 4 NO + 6 H2O)
- high endothermic compound ( BH = 180.6 kJ/mol),
molecule contains one unpaired electron = free radical (!)
- colourless, high toxic gas, low solubility in water
- melting point: - 163.6 C, boiling point: - 151.8 C
- dimerises especially in solid and liquid state to N2O2,
- rapid oxidation to NO2 under presence of air
(< 650 C equilibrium limited reaction)
- supports combustion processes providing its oxygen
- forms nitrosyl compound with halogens (NO-X and NOF3)
- NOx removal from waste gases by SCR with ammoinia or
by reaction with CO and hydrocarbons (3 way catalyst)
Nitrogen dioxide NO2 /dinitrogen tetroxide (O2NNO2)

- formed by NO oxidation at moderate temperatures
2 NO + O2 2 NO2 + 114.2 kJ/mol
- in equilibrium with N2O4
2 NO2 (brown-red) N2O4 (colourless) + 57,2 kJ/mol
- characteristic odour, high toxicity
- melting point: - 11.2 C (0.01 % NO2/99.99 N2O4),
boiling point: +21.2 C (20 % NO2/80 N2O4)
- oxidation agent stronger than N2O and O2, supports combustion
- forms nitryl compounds (O2N-X) with halogens
Industrial manufacturing of Nitric Acid
OSTWALD Process (3 step process for 50 - 68 % acid)

(1) catalytic combustion of NH3 over Pt-Rh alloy gauzes
( short contact times) at 820 950 C and 1 12 bar
4 NH3 + 5 O2 4 NO + 6 H2 O + 904 kJ/mol
(2) further oxidation of NO to NO2 /N 2O4 at ca. 150 C
2 NO + O2 2 NO2 + 114 kJ/mol, 2 NO2 N2 O4 + 57 kJ/mol
(3) absorption in water under presence of excess air
at up to 15 bar: 2 NO2 (=N2O4 ) + H2O + 0.5 O2 2 HNO3
NO
Pt-Rh alloy gauze
air +
ammonia
Direct strong nitric processes for highly concentrated acid (Europe)

- CAN process (Uhde)
(1) catalytic combustion of NH3 at atmospheric pressure
(2) oxidation of NO at 1.6 bar
(3) physical absorption of NO in highly concentrated frozen HNO3
(4) rectification of rough acid to 98 99 % acid (sump)
and N2 O4 (head)
(5) conversion of N2 O4 from (4) with pure oxygen
in diluted HNO3 to 98 99 % acid
- SABAR process (Davy McKees)
(3) absorption of NO in azeotropic HNO3 (68 69 %)
in the presence of oxygen at 6 13 bar
(4) blowing out of the acid with secondary air, acid rectification
(sump: azeotropic acid recycled, head: near pure acid)
Indirect extractive distillation processes (USA)

- sulfuric acid process
counter-current extractive distillation of rough HNO3
(e.g. from Ostwald process) with concentrated H2 SO4
- magnesium nitrate process
distillation of rough HNO3 (e.g. from Ostwald process)
with a 72 % Mg(NO3 )2 solution
Purification of waste gases

- alkali scrubbing with solutions of NH3 , NaOH or urea
- thermal (> 1000 C - NSCR) or catalytic reductive post-combustion (170
600 C - SCR) with reducing agents (e.g. hydrocarbons, hydrogen, CO, NH3 )
Properties and Application of Nitric Acid
Properties
- colourless liquid, decomposes slowly (faster at higher temperatures) to nitrous
oxides and water: 2 HNO3 2 NO2 + H2 O + 0.5 O2
- melting point: - 41.6 C, boiling point: + 82.6 C
- azeotrope with of 69.2 % HNO3 with water (boiling point: 121.8 C)
- azeotrope = traded concentrated HNO3
- strong oxidation agent, reacts with Cu, Ag, Hg, S, P and organic substances (not
with Au, Pt, Rh, Ir)
4 H+ + NO3- + 3 e - NO + 2 H2O
- mixture of HNO3 and HCl (1 : 3) oxidises even oxidises Au
(HNO3 + 3 HCl NOCl + 2 Cl (atomic) + 2 H2 O)
- mixture of HNO3 and H2SO4 (1 : 9) is used as a nitration agent in organic chemistry
- strong acid (pKs = - 1.44)
- salts (nitrates) have a high solubility in water, low melting points (250 350 C)
and decompose easily in the heat:
alkali and earth alkali metal nitrates: KNO3 KNO2 + 0.5 O2,
transition metal nitrates: Cu(NO3)2 CuO + 2 NO2 + 0.5 O2,
ammonium nitrate:
NH4NO3 N2O + 2 H2O + 124.1 kJ/mol (200-260 C) or
NH4NO3 N2 + 0.5 O2 + 2 H 2O + 206.2 kJ/mol (>300 C)
Application
- 75 - 85 % production of ammonium nitrate (NH4NO3)
for fertilizers (80 %), explosives (~ 20 %) and N2O synthesis
(from 50 70 % acid)
- 10 % for production of adipic acid (HOOC-(CH2)4-COOH -
fiber and plastic precursor)
- 3 % production of TNT (with high concentrated acid)
- 3 % nitration of benzene (aniline precursor, reaction is carried out
high concentrated acid)
- 2 % alkali and earth alkali nitrates (fertilisers)
- 1 % organic nitro-compounds
Elementary Phosphorus (1)
Natural sources
- occurs only in compounds
- 0.1 mass % of earth, 13th common element
- inorganic sources: phosphates (apatite Ca3(PO4)2 CaX2 , X = OH, F, Cl;
iron and aluminium phosphates)
- biological importance: participation in metabolism processes as
phosphorus acid esters and phosphates
(e.g. ADP/ATP)
Manufacturing in industry
- highly endothermic electro-thermal reduction of phosphates
with coke and quartz at 1400 1500 C:
1542 kJ/mol + Ca3(PO4)2 + 3 SiO2 + 5 C
3 CaSiO3 (slag) + 5 CO + P 2 (g)
(reduction of P 2O5 by C, SiO2 is added to form a slag with Ca)
- condensation and distillation of rough phosphorus
white phosphorus
carbon electrode carbon electrode

gas outlet (P 2)
phosphatite
outlet
for molten
outlet carbon iron
phosphate
for slags electrodes from
outlet electrode
for slags mass
electrode mass
view from side view from top
Elementary Phosphorus (2)
Modifications
White Red Violet Black

Phosphorus Phosphorus Phosphorus Phosphorus
Manufacture electro-thermal thermal treatment thermal thermal treatment
reduction of of white P treatment of of white P
phosphates at 200-400 C white P at 380 C for
for 20-30 hours at > 550 C some days
(BH = for 1-2 weeks (adding of
- 17.7 kJ/mol) dispersed Hg as
catalyst)
Molecular and P4 tetrahedrons P8 , P8 , P8 ,
crystal structure amorphous complex layer layer structure
structure (similar to
graphite)
Stability meta-stable at meta-stable at 25 meta-stable at stable form
25 C, C 25 C, at < 550 C
thermodyn. thermodyn.
stable at stable
> 620 C at 550-620 C
Melting point 44.3 C sublimation at ~ sublimation at changes to violet
580 C 620 C P
Boiling point 280.5 C - - -
Toxicity high (T+) low low low
Reactivity extremely high, moderate, low, low,
high flammable, heavy reaction flammable at flammable at
strong reducing only with strong > 400 C > 400 C
agent oxidation agents
Metallic/ non- metallic non- metallic non- metallic metallic
non- metallic isolator isolator isolator semiconductor
character,
electrical
conductivity
Phosphorous species in compounds

- occur in all oxidation states from 3 to +5
Application
- 90 % for manufacture of P2 O5 ( phosphorous acid, phosphates)
- synthesis of P-S and P-Halogen compounds ( organic chemistry)
- safety matches (red phosphorous)
- military purposes
Phosphorus Oxides
Phosphorus trioxide (P4O6) and phosphorus pentoxide (P4O10)
phosphorus trioxide (P4O6) phosphorus pentoxide (P4O10)
- manufacture: combustion of P 4 at low temperatures and oxygen

shortage (P4O6) or with dried air under O2 excess
(P4O10)
P 4 + 3 O2 P 4O6 + 1641.2 kJ/mol
P 4 + 5 O2 P 4O10 + 2786 kJ/mol,
separation of oxides by fractioned vaporisation
- properties: P 4O6 white wax-like high toxic solid,
melting point: 23.8 C,
boiling point: 175.3 C (under N2),
oxidation to P 4O10 at temperatures > 70 C
(RH = + 672.4 kJ/mol),
reaction with cold water to phosphonic acid (H3PO3),
with HCl to H3PO3 and PCl 3 and
with halogens to phosphoryl halogenides
P 4O10 white snow-like high toxic solid,
sublimation at 358.9 C,
strong hygroscopic, reacts with water
to phosphorus acid (H3PO4),
very weak oxidation agent (only at high temperatures)
- application: P 4O6 has no technical importance,
P 4O10 is used as a drying and dehydrogenation agent
and (mainly) for the manufacture of phosphorus acid
and its esters.
Phosphorus Acids
Formal Oxidation +1 +2 +3 +4 +5
number of P
-
acids H3PO2 H4P 2O2 (HPO2)n, H4P 2O6 (HPO3)n,
H3PO3, H3PO4,
H4P 2O5 H3PO5,
H4P 2O7,
H4P 2O8
phosphinate phosphonate phosphate peroxophosphate diperoxophosphate
anions of ortho-phosphorus acids

(P=O double bond is delocalised between all P-O baonds)
Deprotonation in water
phosphinic acid (=hypophosphoric acid) = one-base acid
phosphonic acid (= phosphorous/phosphoric acid) = two-base acid
phosphorus acid, peroxophosphorus acid and diperoxophosphorus acid = three-base
acids
hypodiphosphonate diphosphonate hypodiphosphate diphosphate

(diphosphate(III)) (diphosphate(III)) (diphosphate(IV)) (diphosphate(V))
diphosphate(II,IV) diphosphate(III,V) peroxo-

diphosphate(V)
anions of diphosphorus acids
Technical important phosphorus acids: H3PO4, H3PO3 and H3PO2

Phosphorus acid - H3PO4
Manufacturing (I) Wet processes

Dihydrate process (80 C CaSO4 2 H2 O),
hemihydrate process (95 C ) CaSO4 H2O)
Ca3(PO4)2 (apatite) + H2SO4
3 CaSO4 + 2 H3PO4,
concentration of the acid by vacuum
evaporation or submerged burners,
purification of the acid by precipitation and
extraction with organic solvents
(II) Thermal process
Oxidation of white P 4 in air excess and
absorption of the formed P 4O10 together
with water in conc. H3PO4 (85 %)
P 4 + 5 O2 P 4O10, P 4O10 + 6 H2O 4 H3PO4
(single tower IG process,
double tower TVA process)
Properties pure acid = colourless, clear, odourless hard solid,

melting point: 42.4 C,
partially condensation (at 200 C completely)
2 H3PO4 H4P 2O7 + H2 O
concentrated (85 %) acid = high viscous liquid,
melting point: 21.1 C, boiling point: 158 C,
three-base middle-strong acid
(pK S1 = 2.16, pKS2 = 7.21, pK S3 = 12.32),
pure acid = strong oxidation agent > 400 C,
diluted acid = no oxidising properties
buffer area
pH
Application producing of salts (phosphates of K, Na and NH4),

use of acid itself in cleaning agents, in metal treatment and
polishing, as an acidification agent in soft drinks (colas,
lemonades),
organic chemistry (e.g. esterification)
H3PO3 and H 3PO2
Ortho-phosphorous/ortho-phosphoric/ortho-phosphonic acid (H3PO3)

- manufacture: (I) PCl 3 + 3 H2O H3PO3 + 3 HCl at 190 C
(II) P 4O6 + 6 H2O 4 H3PO3
- properties: colourless crystals, melting point: 73.8 C,
middle-strong two base acid (pK S1 = 2.0, pK S2 = 6.6),
in aqueous solutions high solubility of alkali salts,
phosphoric acid
low solubility of other salts,
hydrogen phosphonates dimerise in the heat
2 H2PO3- (HO2POPO2H) 2- + H2O,
strong reducing agent, reduce noble metals from
their salts, halogens to halogenides, H2 SO4 to H2SO3,
stable under air atmosphere at room temperature
phosphonic acid
disproportionation at heating of the dry acid
Organyl derivates are known 4 H3PO3 PH3 + 3 H3PO4 (130 140 C)
from both tautomeric forms .
- application: reducing agent, industrial synthesises of base
lead phosphonate (PVC stabilisator), of organic
phosphonic acids and phosphorous acid esters
Ortho-phosphinic/ortho-hypophosphoric acid (H3PO2)
- manufacture: (I)
Cooking of white P 4 with NaOH or Ca(OH) 2
2 P 4+ 3 Ca(OH) 2 + 6 H2O
2 PH3 + 3 Ca(H2PO2)2
hypophosphoric acid Ca(H2PO2)2 + H2SO4 CaSO4 + H3PO2,
isolation by vaporising of the solution
or by extraction with diethyl ether
(II) PH3 + 2 I2 + 2 H2O H3PO2 +4 HI
(III) treatment of P 4 with warm water
phosphinic acid
(disproportionation)
Organyl derivates are known P 4 + 6 H2O PH3 + 3 H 3PO2
from both tautomeric forms .
- properties: colourless flakes, melting point: 26.5 C,
middle-strong one base acid (pK S = 1.23),
acid and salts are strong reducing agents
reduce noble metals from their salts,
disproportionation in warm water:
3 H3PO2 PH3 + 2 H3PO3 (130 140 C),
in strong base solutions: H2PO2- + OH- HPO32- + H2
- application: deposition of Ni from salts
on metals (pH = 4 6, 90 C), plastics and other
non-conductors (pH = 7 10/25 - 50 C)
Salts and Organic Compounds from Phosphorus Acids (1)
Fertilizers - general importance

- Plants need for growing not only light, air, warmth and water, but additionally S, P,
N, K, Ca, Mg and Fe
- Harvesting removes especially N, K, P and Ca (no back mineralisation can occur
returning the minerals to the soil, only Fe is present in excess)
- Minerals can be re-added by fertilising, especially K, N and P. Solubility of the
minerals in water decides about availability for the plants:
high solubility fast availability, but rapid washing out,
low solubility low, but continuous availability
long time supply
Manufacture of inorganic phosphates and other fertiliser salts

- phosphates/phosphites/fertilizer sulphates:
neutralisation of NaOH, KOH, CaO or NH3 with phosphorus acid
(phosphates), phosphorous acid (phosphites) or sulphuric acid
(sulphates), precipitation and metathesis reactions
- diphosphates and polyphosphates
thermal treatment of phosphate mixtures (condensation -
e.g. 2 Na2HPO4 Na2H2P 2O7 + H2O), reaction time and
temperature (250 - 900 C) control polymerisation degree
Salts mainly used for fertilisation

- phosphates: superphosphates, obtained by treatment
of Ca3(PO4)2 (low solubility) with 50 % H2SO4
= mixture of Ca(H2PO4)2 (high solubility) and CaSO4
superphosphate 16 22 % P 2O5,
double superphosphate 35 % P 2O5,
triple superphosphate > 46 % P 2O5
ammonium phosphates (made by neutralisation and
thermal condensation), used purely and
in H2 O solution (high solubility)
Rhenania phosphates made by sintering of apatite
with silica and Na2CO3 or NaOH (29 % P 2O5,
low solubility)
Melt phosphates made by melting apatite with
Mg compounds and silica (21 % P 2O5, low solubility)
Thomas phosphates = slag from smelting
P containing iron ores (10-18 % P 2O5, low solubility)
- ammonium nitrate/ammonium sulphate (made by neutralisation)
- urea (made by CO2 + NH3 NH2COONH4 OC(NH2)2 + H2O)
- potassium chloride (mining), sulphate and nitrate (KCl + H2SO4/HNO3 or nitrates)
Salts and Organic Compounds from Phosphorus Acids (2)
Non-fertilizer applications of inorganic phosphates

- sodium phosphates (general)
metal cleaning, phosphatising, boiler water treatment,
buffer systems, food production, nutritional supplement in animal
feedstuffs
- disodium dihydrogen phosphate, calcium phosphates
baking powder (additionally Ca3(PO4)2)
- tetrasodium phosphate
industrial cleaning agent
- sodium polyphosphates
added to reconstituted cheese, condensed milk, sausages,
used for stabilisation of pigment suspensions and
in leather tanning
- ammonium phosphates
fire protection, intumescent paints, animal feedstuffs
- tetrapotassium diphosphate
liquid cleaners
- calcium phosphates
nutritional supplement, baking powder,
cleaning agent in toothpastes
NOTE: Use of phosphates for cleaning applications is decreased,

because of anthropogenic phosphate entries to natural rivers and lakes causes
euthrophication.
Organic Derivates from Phosphorus Acids

- phosphoric acid triesters
flame retarding plasticiser, hydraulic fluids, anti-foaming agents,
stabilisators
- phosphorus (V) ester acids
anti-static agent, cleaning agents, dishwasher liquids
- thiophosphoric acid derivates
herbicides (e.g. Malathion, Parathion),
Zn salts are additives for lubricant oils
- amino-methylene phosphonic acid and hydroxy-ethane diphosphonic acid
detergent additives to prevent Ca precipitation in washers
- aromatic phosphorous acid esters
antioxidants, stabilisers in plastics, rubber and lubricant oils
- aliphatic phosphorous acid esters
starting materials for insecticides and veterinary products
Other Industrial Important Phosphorus Compounds (1)

Phosphorus halogen compounds
- PX3, P 2X4, PX5, POX3, PSX3 (X = F, Cl, Br, I), P 4F6, P 6Cl6, P 6Br6
- mixed halogen compounds and partial substitution of halogens by hydrogen are
possible
- technical importance: PCl 3, PCl 5 and POCl 3
- synthesis:
PCl 3 direct conversion of white phosphorus with dry chlorine
P 4 + 1.5 Cl 2 PCl 3 + 320 kJ/mol
PCl 5 chlorine addition to PCl 3, PCl 3 +Cl 2 PCl 5 + 124 kJ/mol
POCl 3 oxidation of PCl 3 with oxygen at 50 60 C
PCl 3 +1/2 O2 POCl 3 + 277.6 kJ/mol,
synthesis from P 4O10 and PCl 3
P 4O10 + 6 PCl 3 + 6 Cl 2 10 POCl 3
PSCl 3 PCl 3 +S PSCl 3 in autoclaves at 180 C
- properties:
PCl 3 colourless, smoking, toxic liquid with stabbing odour,
hydrolysis in water to H3PO4 and HCl, Lewis base properties,
moderate reducing agent
PCl 5 green-white toxic solid, decomposes at higher temperatures
into PCl 3 and Cl 2, in the presence of water
via POCl 3 + HCl to H3PO4 and HCl,
Lewis acid
POCl 3 colourless, smoking, toxic liquid
PSCl 3 colourless liquid,
melting point: -35 C, boiling point: 125 C,
decomposes with water to H3PO4, HCl and H2S
- use:
PCl 3 synthesis of H3PO3 (10 %) and alkyl substituted phosphates
(detergents), of PCl 5, POCl 3 (33 %) and PSCl 3,
starting material for ligand compounds
in metal-organic chemistry
PCl 5 chlorination agent in organic chemistry
POCl 3 manufacture of POX derivates (X = -OR, -NHR, -R)
used as lubricant additives, softeners,
flame inhibitors and insecticides
PSCl 3 manufacture of thiophosphoric acid ester chlorides
for the production of pesticides
Other Industrial Important Phosphorus Compounds (2)
Phosphorus hydrogen compounds (phosphanes)

- PH3, P 2H4, P 3H5 (linear compounds), P 5H5, P 7H3 (cyclic compounds)
with P as the electronegative partner
- PH3 exothermic compound, all other P xHy are endothermic compounds
- Technical synthesises of PH3:
(1) P 4 + 3 NaOH + 3 H2O PH3 + 3 NaH2PO2
(2) 2 P 4 + 12 H2O 5 PH3 + 3 H3PO4
- Properties of PH3:
colourless, toxic gas with garlic odour,
low solubility in water, neutral reaction
(pK B (PH3/PH4+)= 27, pKS (PH3/PH2-) = 29),
salts: phosphides P 3- (wide variety of higher phosphides from P xHy)
decomposes at higher temperatures into the elements,
stronger reducing agent than NH3
- Use:
Manufacturing of light emitting diodes, doping of silicium,
organic synthesises,
important substance in metal-organic chemistry of complexes
Phosphorus sulphur and selenium compounds

- composition: P 4Sn (n = 2 10), PSn (phosphorus polysulphides),
different thiophosphates (linear compounds),
P 4Sen (n = 3-5), P 2Se5
- manufacture: fusing of P 4 and S/Se, exothermic reactions;
seperation by extraction with CS2,
com- and disproportionation reactions
- application: P 4S10 has some technical importance
(flotation agent, lubricant additive,
manufacture of insecticides)
Phosphorus nitrogen compounds

- polymeric (NPCl 2)n
Substitution of Cl atoms by organic groups (-OR, -NR2, -R) gives
polymers with properties between caoutchouc and high severity.
These polymers are used for fibres, textiles, foils and hoses.
(NP-O-CH2-CF3)n polymers are used in surgery for artificial organs
and chirurgical threads.
Arsenic, Antimony and Bismuth
Arsenic
- natural sources: primarily sulphidic and arsenidic ores, rarely oxidic ores and in
elementary form (often mixed with antimony)
- two modifications:
(I) grey rough metallic arsenic As 8 - stable form,
conducts electricity (semi-conductor)
(II) black antimony As 8 - amorphous As modification,
electrical isolator, stable until 270 C
(III) yellow non-metallic arsenic As 4
electrical isolator, stable only at low temperatures and in the
absence of light, converts to grey arsenic in the presence of
light even at 180 C
- As compounds are essentially in very low, but high toxic in higher concentrations
(As(III) - the poison of the middle age)
- used for metal alloys especially with copper and lead (letter metals, lead
accumulators), for electronic pieces (alloys with Ga and In), and in pesticides
Antimony
- natural sources: primarily sulphidic ores, rarely oxidic ores and in elementary form
(often mixed with arsenic)
- two modifications:
(I) grey rough metallic antimony Sb - stable form,
conducts electricity (semi-conductor)
(II) black antimony Sb8 - amorphous Sb modification,
electrical isolator, stable only below 0 C
- Sb compounds are high toxic (similar to arsenic)
- used for metal alloys especially with tin and lead to increase roughness and for
electronic pieces
Bismuth
- natural sources: sulphidic and oxidic ores
- non-toxic rough semi-metal (not essential for biological processes)
- used for metal alloys with low melting temperatures (< 100 C),
e.g. applied in electrical fuses
Chapter 8
Carbon Group
Group Members Carbon Silicon Germanium Tin Lead

(C) (Si) (Ge) (Sn) (Pb)
Rel. Atomic 12.01 28.09 72.59 118.69 207.2
Mass
Discovery unknown 1824 Berzelius 1886 known since unknown
Winkler antique
Percentage on 0.02 26.3 1.4 * 10-4 2 * 10-4 1.2 * 10-5
earth
[Mass-%]
density [g/cm] 3.51 2.32 5.32 7.28 11.34
(diamond)
2.26
(graphite)
melting point 2250 1410 937.4 231.9 327.4
[C] (sublimation)
boiling point 2477 2830 2687 1751
[C]
state at room colourless dark-grey, grey-white, silver-white, blue-grey,
temperature (25 diamond , hard, brittle very brittle very soft very soft
C) polymeric metal metal metal metal
and 1 bar black graphite,
fullarenes
Electron 2.5 1.8 1.8 1.8 1.8
negativity
valence numbers -4+4 -4+4 -4+4 -4+4 +4 (+2)
in compounds
Reducing/ oxidising reducing
Oxidation Power power power
Metallic/ Non- non-metallic
metallic (diamond),
semimetallic semimetallic metallic metallic
character semimetallic
(graphite)
Electrical isolator
conductivity (diamond),
semi -conductor semi -conductor conductor conductor
semi -conductor
(graphite)
Acid/Basic
primarily
properties of acid acid amphoteric amphoteric
base
oxides
Stability of
valence states
4
+2
+4
Physiology base of life essentiell not essential, essential toxic
non-toxic
Electron configuration: sp2 (d10 ) need of accepting or loosing

4 electrons for full saturation of electron shells
General Properties of Carbon Group Elements
Valence states:
- - 4 with electropositive elements (known of all elements,
stability decreases with increasing period number)
- + 2 and + 4 (+4 is favoured for C, Si, Ge and Sn, + 2 for Pb)

- formation of monomeric (XH4), polymeric (XnH2n+2 C, Si, Ge)
and cyclic (C, Si) hydrogen compounds
CH4 ( B H = 75 kJ/mol) > SiH4 (+34 kJ/mol) > GeH4 (+91 kJ/mol)
> SnH4 (+163 kJ/mol) > PbH4 (+278 kJ/mol observed only in traces)
- bonding energy H-X decreases
CH4 (416 kJ/mol) > SiH4 (323 kJ/mol) > GeH4 (289 kJ/mol)
> SnH4 (253 kJ/mol)
Halogen compounds
- C and Si: substitution of hydrogen atoms by halogens
- Ge, Sn and Pb: XHal 2 and XHal 4 compounds
Oxygen compounds and binary compounds with higher chalkogenes

- C: CO and CO2 (with higher chalkogenes CY2)
- Si: non-stable SiO and polymeric (SiO2)n
(with higher chalkogenes primarily SiY2)
- Ge, Sn and Pb: XO and XO2 compounds
(with higher chalkogenes XY and XY2, only PbS)
Acids/Bases
- C: non-stable H2CO3 acid properties
- Si: monomeric H4SiO4 (only stable salts) - acid properties,
condensation to polymeric acids (SiO2 (n<2) H2O) m
- Ge: H2GeO2 and H4GeO4 (stable only in salts or in dilution)
acid properties
- Sn: Sn(OH) 2 and Sn(OH) 4 amphoteric properties
Pb: Pb(OH) 2 base reaction in H2O,
plumbites in strong base solutions,
Pb(OH) 4 non-soluble in water, weak amphoteric properties
Pb(IV) salts in acid solutions, plumbates in base melts
Elementary Carbon
Natural sources
- elementary: diamonds (Africa, Brazil, Siberia)
graphite (Madagascar, Sri Lanka, Korea, Norway etc.)
- in compounds: carbonates (lithosphere, hydrosphere),
organic compounds (biosphere);
carbon dioxide (atmosphere 0.03 %, hydrosphere)
Modifications
dia
liquid
mo
diamond carbon
nd
/m
gra
elt
ph
ite
/m
elt
(m
eta
pressure
- sta
ble
)
diamond
mond gaseous
ite /dia
graph graphite carbon
temperature
diamond graphite p-T diagram of carbon
- diamond: - colourless non-metallic modification,

- electrical isolator
- high hardness (used for tools)
- manufacture: mining or treating of graphite
at high temperatures and extreme pressures
- graphite: - grey-black semi-metallic modification
with metallic brilliance
- consists of hexahedron layers,
connected by delocalised electrons
- conducts electricity
- extreme resistance against thermal stress
- conversion to (synthetic) diamond at 1500-1800 C
and 53000-100000 bar (R H = + 1.9 kJ/mol)
- manufacturing by mining of natural graphite
(purification by flotation) or thermal treatment
of coke, mineral oil or natural gas at 600-3000 C
- - application: manufacturing of fire-resistant products,
electrodes, paints, pencils, use as lubricant and
as moderator/reflector in nuclear rectors
Special Types of Graphite
soot: low order layer structure

from low temperature treatment (400-600 C)
synthetic electro graphite: high order layer structure

from high temperature treatment
(2600-3000 C)
carbon fibres: - obtained by pyrolysis of polyacrylnitrile

at 2500-3000 C,
- high tensile strength and elasticity
activated carbon: - microcrystalline, highly porous graphite

(inner surface > 1000 m/g)
- obtained by activation of carbon
with steam, air or CO2 at 700-900 C
(burning of pores)
fullerenes: - Cn clusters, n = 60, 70, 76, 78, 84, 90, 94, ,

- footballs, formed by side-by-side
connected pentagons,
- yellow-brown crystals with lower density
than graphite
- formed by vaporisation and rapid cooling
of graphite
- stable in air and water
Fullarene-60
Hydrocarbons and Halogenated Hydrocarbons
straight and branched aliphatic compounds with only single C-C bonds
(saturated hydrocarbons)
methane ethane propane isobutane C4 H10

butane
straight and branched aliphatic compounds with multiple C-C bonds

(unsaturated hydrocarbons - olefins)
ethylene C 2H4 propylene C3H6 butadiene C4H6 acetylene C2H2 propine C3H4
cyclic compounds aromatic compounds
cyclohexane cyclopentadiene benzene naphthalene anthracene
subject of organic chemistry, more than 106 compounds
Partially and fully halogenated hydrocarbons compounds

- manufactured by
(1) substitution reactions with halogens Y2 (-HY)
(2) addition reactions with halogens (Y2 )
or halogen hydrides (HY) to unsaturated hydrocarbons
- light halogenated hydrocarbons are used as solvents, blowing agents and in refrigerators
and air conditioning systems (low reactivity)
use of Cl and Br substituted hydrocarbons is restricted by
the Montreal protocol (ozone depleting effect in stratosphere)
- use in many organic synthesis (herbicides, intermediates to substitute functional groups)
Carbon Oxides
Carbon monoxide (CO)
- Manufacture:
- thermal treatment of coke with air at 1000 C
( Boudouard equilibrium),
- laboratory scale: decomposition of formic acid by conc. H2SO4
HCOOH CO + H2O
- Properties
colourless, odourless, toxic and burnable gas,
melting point: - 205.1C, boiling point: -191.5 C,
low solubility in water (0.35 l/l H2O at 0 C),
triple bond between C and O
- Application
- synthesis gas = CO/H2 mixtures for manufacture of
a large number of industrial chemicals
- reducing agent (iron metallurgy - in-situ formation
from coke and air in the kiln)
one of the most important industrial chemicals
Carbon dioxide (CO2)
- Manufacturing
(1) oxidation of coke in oxygen/air excess
(2) by-product of lime manufacturing
(2) treating carbonates with mineralic acids (laboratory scale)
- Properties
colourless, non-burnable gas with acid odour,
sublimation at 78.5C (1 bar),
liquefaction only at higher pressures (5.3 - 76.3 bar)
low solubility in water (0.9 l/l H2O at 20 C) acid reaction,
poor reactivity, weak oxidation agent
in concentrations > 5 % toxic for humans and animals,
essentially for plants
- Application
inert gas,
blowing agent,
freezing agent (dry ice),
neutralisation agent,
sparkling agent in soft drinks
Industrial Carbon Oxide Chemistry (1)
Resources
- mineral oil: - mixture of middle-heavy hydrocarbons, fractionated by
rectification (light gasoline 30-100 C,
heavy gasoline 100-200 C, light oil 200-250 C,
diesel, heavy oil 250-350 C, tar - >350 C)
- Natural gas: - CH4 (80 %), C2H6, C3H8, C4H10, C5H12,
impurities of H2S, CO2, N2 and He
- Coal: - complex mixture consisting of a large amount
of organic (primarily poly-aromatic) compounds,
contains C, O, H, N and S,
- brown coal: 65-75 % C, stone coal: 75-90 % C,
anthracite: > 90 % C
Gasification of coal Boudouard equilibrium
- Reactions
- Equilibrium plot
temperature
- conversion of coal is performed at 1000 C in Winckler generators
- product mixture = generator gas (70 % N2, 25 % CO and 4 % CO2)
Synthesis Gas
- Composition: - mixture of N2, CO, CO2, H2 and H2O,

ratio depends on demand and
is controlled by temperature,
- Water gas = 50 % H2, 40 % CO, 5 % CO2,
4-5 % N2, traces of CH4
- Equilibrium Reactions:
temperature
- Manufacture (for details see ammonia synthesis Chapter 7):

(1) Steam reforming of natural gas, naphtha, water
2 C2 H2n+2 + n H2 O n CO + 2(n+1) H2
(2) Partial Oxidation of heavy fuel oil
2 C2 H2n+2 + n O2 2n CO + 2(n+1) H2
(3) Coal gasification
C + H2O CO + H2, 2 C + O2 2 CO,
Synthesis Gas
- Application:
ammonia
urea resins
synthesis
oxidation
formaldehyde polyols
paraffins
acetates
coal olefins
alcohols acetic acid

anhydride (ESA)
methanol
synthesis
synthesis gas
(syngas) ethylene
aromatic comp.
poly-
polymethylene Mobile process
merisation
min. oil/ olefins
nat. gas metha-
nisation fuels
process
+ isobutene
methyl-tert-
oxo-aldehydes buthyl-ether (MTBE)
oxo-
synthesis
fermentation
oxo-alcohols
Further Important Carbon Compounds
Carbides
- compounds with electropositive elements (anions C4-, C22-)
- formed at 2000 C
from the elements,
from element compounds (especially oxides) + carbon,
from element + hydrocarbon and
from element compounds+ hydrocarbon
- ionic (saltlike), covalent and metallic carbides
- saltlike carbides MC 2 : hydrolysis to acytelene (e.g. CaC2 )
- covalent carbides MC: high thermal resistance and hardness,
structures and properties similar to diamond
(e.g. SiC, boron carbides)
- metallic carbides: with C and transition metals (IVb-VIb groups)
high thermal resistance (melting points of 3000-
4000 C), hardness similar to diamond,
conduct electricity, metallic brilliance
Hydrogen cyanide (HCN), Cyanides

Manufacture
(HCN): (I) Degussa process (1200 C, Pt catalyst)
CH4 + NH3 HCN + 3 H2
(II) Andrussow process (1200 C, 2 bar, Pt/Rh cat.)
CH4 + NH3 + 1.5 O2 HCN + 3 H2O
cyanides: neutralisation with HCN
Properties (HCN): inflammable and high toxic gas,
soluble in water (weak acid reaction, Ks = 2.1 10-9 ),
complexing agent
Application: galvanisation (salts), gold mining and extraction,
processes in organic chemistry,
e.g. methyl methacrylate (acid and salts)
Phosgene (COCl2 )
Manufacture: CO + Cl2 COCl2 at 720-750 C
Properties: highly reactive and high toxic gas
Application: synthesis of poly- urethanes,
chlorination agent for metal oxides (e.g. SnO 2 SnCl4 )
Carbon disulfide CS2

Manufacture: (I) C + S2 CS2 at 720-750 C
(II) CH4 + 2 S2 CS2 + 2 H2S at 650-750 C
Properties: endothermic liquid, inflammable and high toxic
Application: viscose industry (rayon), cellophane production,
synthesis of CCl4 ,
production of vulcanisation accelerators,
flotation agents, corrosion inhibitors, herbicides and
pharmaceuticals
Elementary Silicon (1)
Natural sources
- second most common elements
- minerals: quartz sand (SiO2), silicates
Manufacturing of the metal

- metallurgical grade Si: thermal treating of quartz with coke
in an electrical furnace
(at 2000 C for 1-2 h, R H = 690.4 kJ/mol)
SiO2 + C SiO + CO
SiO + 2 C SiC + CO
2 SiC + SiO2 2 Si + 2 CO
- electronic grade Si: - purification of metallurgical grade Si by
(1) conversion into SiHCl 3 (300 C)
Si + 3 HCl SiHCl 3 + H2
(2) Distillation of SiHCl 3
(3) decomposition of SiHCl 3 at 1000 C
yielding to highly purified Si
SiHCl 3 + H2 Si + 3 HCl
- formation of singly crystals by zone melting
- zone melting in presences of traces
of volatile compounds of the dopant or
by thermo-neutron bombardment (Si P)
-
Elementary Silicon (2)

Properties
- dark-grey, hard, brittle metal, semi-conductor
- lattice structure similar to diamond
- metallurgical grade Si: 98.5-99.7 %
- electronic grade Si: >99.999 %
- reacts with electronegative elements only at high temperatures (exothermal
reactions, but passivation, with O2 at 1000 C,
with N2 at 1400 C, with S at 600 C, with C at 2000 C, only with F2 at room
temperature)
Application
- component of steel
- special alloys with iron (ferrosilicon, 8-13 % Si, 87-95 % Fe)
- alloys with Al, Cu and Ti
- semiconductor components (diodes, transistors, electronic circles, processors, solar
cells)
Hydrogen Silicon Compounds
straight and branched aliphatic compounds with only single Si-Si bonds
(saturated silanes)
monosilane disilane trisilane n

tetrasilane iso-tetrasilane polysilane
H3Si-(SiH2 )n-SiH 3
cyclic compounds (Si > 4)
cyclopentasilane cyclohexasilane
no Si multiple bonds (no formation of - bonds)

no stable unsaturated or aromatic compounds
wide variety of compounds,

similar reactions to organic chemistry
Monosilane SiH 4 :
- manufacture: (1) decomposition of Mg2 Si with acids
in the absence of air
Mg2 Si + 4 H+ SiH4 + 2 Mg2+
(2) hydrogenation of SiCl4 with LiH
in molten LiCl/KCl at 400 C
SiCl4 + 4 H- SiH4 + 4 Cl-
- properties: - endothermic colourless gas
- melting point: -184.7 C, boiling point: -112.3 C
- stable up to 300 C in the absence of air,
than decomposes to Si and H2
- under air: inflammable,
SiH4 + 2 O2 SiO 2 + 2 H2 O + 1518 kJ/mol
- in the presence of water:
SiH4 + 2 H2 O SiO 2 + 4 H2 + 374 kJ/mol
- with halogens and hydrogen halogenides
stepwise replacing of H by Hal
- application: manufacture of ultra pure Si
Technical Important Binary Silicon Compounds
Silicon halides:
- SiF 4 manufacture: CaF2 + H2 SO4 2 HF + CaSO 4
SiO 2 + 4 HF SiF 4 + 2 H2 O (in conc. H2 SO4 )
properties: - highly exothermic compound, stable under dry air,
decomposes in water:
3 SiF 4 + 2 H2 O SiO 2 (aq) + 2 H2 SiF 6
application: hydrolysis HF manufacture
- SiCl4 : manufacture: Si + 4 HCl SiCl4 + 2 H2 /
Si + 3 HCl SiHCl3 + H2 (300 C)
properties: colourless, smoking liquid with sticking odour
application: - manufacture of electronic grade Si
- synthesis of organic silicon compounds
- siliconisation of metallic surfaces
- manufacture of highly dispersed SiO 2
Silicon dioxide (SiO 2 ) quartz

- manufacture: - mining of quartz sands, re-crystallisation in H2 O
- - flame hydrolysis of SiF 4 and SiCl4
- properties: - high stable, exothermic solid
- crystal and glass (amorphous) modification
- reacts only with HF at room temperature,
- reacts with alkali hydroxides in molten state
- application: - glass industry, foundries, chemical apparatus
- manufacturing of silicates, of enamels, of ceramics
and of SiC
- polishing agent, inorganic filler
- piezoelectrical effect use in quartz watches
Silicon nitride (Si3 N4 )

- manufacture: (1) from the elements at 1100-1400 C
3 Si + 2 N2 Si3 N4 + 750 kJ/mol
(2) 3 SiO 2 + 2 N2 + 6 C Si3 N4 + 6 CO
(3) 3 SiCl4 + 4 NH3 Si3 N4 + 12 HCl
- properties: - colourless solid with high hardness
but low density
- stable up to 1900 C
- resistant against corrosion and mechanical stress
- application: - special ceramics
- manufacturing of chemical apparatus,
high quality mechanical tools
- mechanical and motor engineering
- fittings
Silicon carbide (SiC): see carbides under

Further Important Carbon Compounds
Metal Silicides: metallic hard materials

Silicon Acid and Silicates
Manufacture: - Silicates:
melting of alkali carbonates or hydroxides
with quartz sand
- Acid: (1) solving alkali silicates in H2 O and
precipitation of the acid by slow acidification
(2) hydrolysis of monomeric SiX4 compounds
SiX4 + 4 H2O H4SiO 4 + 4 HX
Properties: - weak acid, meta-stable only in dilution
- condensation = tri-dimensional polymerisation
(1) initial reaction
Polymerisation goes via micro-particles (sol) to a highly viscous

silicon acid/water mixture (gel) to crystalline SiO2.
(2) secondary structure
chains bands layers
- determining structure by blocking of polymerisation sides by metal

cations
- base unit: SiO4 tetrahedrons, coupled by corners, edges and surfaces
Application: - glass and alkali silicates

- zeolithes (with AlO4- salts)
- glass fibres
- cement (CaSiO3)
- natural and synthetic fillers
Glassware
Starting materials: - quartz sand

- soda ash and potash, Glauberss salt
- lime
- lead oxide
- borax
- kaolin and feldspar (Al)
Manufacture: melting of the mixture of starting materials at 1200-1650 C

and stepwise careful cooling with homogenisation
Properties: - amorphous mixed silicates, freezed melt

- high thermal and chemical resistance
- good electrical isolator
- softening temperature
between 550-650 C (soda-lime glass) and 2000 C (quartz)
Composition of typical glassware:

Zeolithes
Manufacture: - from natural zeolithes (e.g. kaolin)

- conversion by shock-heating at > 550 C,
followed by suspension in NaOH solution at 70-100 C,
product: zeolithe A (ion exchanger in for detergents)
- synthetically by common precipitation from
Na water glass and NaAl(OH) 4 solutions
at high temperatures and partially high pressures
- synthetically by sol-gel techniques
(in alcohols with metal alcoxides as initiators)
Structure: - consisting of (SiO4) and [AlO4 ]- tetrahedrons with large,

but specific cavities
- cations are delocalised in the cavities and
can be exchanged by other cations
Elementary cell of sodalithe Tertiary structure of zeolithe A
Application: - ion exchangers (e.g. in detergents)

- molsieve (after thermal treatment at 400-550 C
to remove water from the cavities)
- specific adsorption agent
- catalyst (cracking and isomeristaion of hydrocarbons)
and catalyst support (high specific surface areas)
Silicones (1)
Manufacturing:
Precursors:
- (chloro)methylsilanes
- (chloro)phenylsilanes
- obtained by Rochow Mller process

- (300/500 C, CuO catalyst,
ZnO as an activator)
Si + 2 CH3 Cl (CH3)2SiCl 2
Si + 2 PhCl Ph2-SiCl 2
Polymerisation:
- hydrolysis of products in 25 % HCl at 100 C
gives cyclic and linear siloxanes (1:1 1:2)
- ring opening with KOH or with strong minaralic
acids (H2 SO4 )
Silicon oils
Molecular structure: linear polysiloxanes

Properties:
- thermal stability (300 C)
- viscosity only poor dependent from
temperature
- high electrical resistance
- low surface tension
- odourless, tasteless, physiologically inert
Application:
- heat transfer media, lubricants, hydraulic oils, transformer oils,
brake fluids, paint flow improvers, gloss improvers, defoaming agents, mold
releasing agents, component of skin creams and protective polishes
Silicones (2)
Silicone Rubbers
- crosslinked polysiloxanes
- application: sealing compounds in the construction industry,

in sanitary sector, glass sector and automobile
industry, adhesives for heat-resistant bonds and seals
Silicon Resins
- poly-organosiloxanes with a high portion of branched
tri- or tetrafunctional siloxy groups
- thermal stable, weather resistant, hydrophobic
- application: electrically insulating lacquers,
corrosion protection lacquers
(pigmented with zinc dust),
stoving enamels,
coil coating of metallic plates for facades,
rendering plastics scratch resistant
Germanium
Natural sources
- rather seldom sulphidic minerals (not in technical use)

- outgoing from waste gases of Zn manufacture
- Process steps:
(1) extraction GeO2 and ZnO of fly ash with H2 SO4
(2) precipitation of oxides at pH = 5 with NaOH
(3) conversion of oxides to chlorides with HCl
(4) distillation separation of GeCl 4 and ZnCl 2
(5) Hydrolysis of GeCl 4 to GeO2
(6) reduction to Ge with H2
- high purity Ge (electrical grade) is obtained by zone melting
Properties of the metal

- grey-white, very brittle metal with semi-conductor properties
- stable under air, in water, in base solutions and in non-oxidising acids
- transformation to GeO2 by concentrated H2SO4 and HNO3
Application of the metal

- transistors
- optical lenses, prisms, windows (high IR transparence)
- special alloys and superconductors
Germanium compounds
- typical reactions and compounds of IVa group elements
- oxidation state + 4 is favoured compared to + 2 (both are stable)
- amphoteric (predominantly acid) character of hydroxides
- no technical importance of single compounds
Tin
Natural sources
- occurs primarily in form of sulphidic and oxidc ores
- minor amounts of elementary metal

- thermal reduction with coke
360 kJ/mol + SnO2 + C Sn + 2 CO
- recycling of tinplate wastes in an electrochemical process

- silver-white, very soft metal with conductor properties
- essential, non-toxic
- high stability under air (reacts only in the heat) and in water
- oxidised by hot strong base solutions (forming stannates(IV))
and by concentrated acids (forming Sn(II) salts

- dishes
- corrosion inhibitor for iron sheet metals by impregnation with molten Sn
(forming tinplate)
- solder tin (alloy with 30-60 % lead, eutectic point)
Tin compounds
- oxidation state + 4 is favoured compared to + 2 (both are stable)
- SnCl 4: - obtained from the elements by treating of tinplate wastes

with chlorine: Sn + 2 Cl 2 SnCl 4 + 511.6 kJ/mol
- colourless smoking liquid, Lewis acid properties
- used as homogeneous Friedels-Crafts catalyst and
for synthesis of organic Sn compounds
- SnO2: - white pigment for glazes and enamels
- organic Sn compounds:
- partially high toxicity
- use as PVC stabilisator, for vulcanisation of silicones,
as biocides and anti-fouling paints
Lead
Natural sources
- occurs primarily in form of sulphidic ores

- roast reduction process
PbS + 1.5 O2 Pb + SO2
PbO + CO Pb + CO2
- roast reaction process
3 PbS + 3 O2 PbS + PbO + 2 SO2
PbS + 2PbO 3 Pb + SO2
- purification by melting with air or by electrochemical process
(enrichment of silver impurities)
- recycling of accumulators

- blue-grey, very soft metal with conductor properties
- non-essential, but high toxic
- high stability under air (passivation, reacts only in the heat)
oxidised in oxygen-containing water
- oxidised by base solutions (forming plumbites(II))
and by acids (forming Pb(II) salts, but passivation by low-soluble salts PbSO4,
PbCl 2, PbF2)
- absorption of radioactivity
-
- tanks for strong corrosive
chemicals charging
energy
dis-charging
- accumulators
- liquid in heating baths electrons
- protection against radioactivity

- alloys with antimony high
mechanical strength used for
bearings
Lead compounds
- oxidation state + 2 is favoured compared to + 4
(strong oxidation agent)
- PbO PbO2: - used in glass manufacture, corrosion inhibiting paint

- lead salts: - oxides and chromate are used in oil paints
Chapter 9
Earth Metals
(Boron Group)
Group Members Boron Aluminium Gallium Indium Thallium

(B) (Al) (Ga) (In) (Th)
Rel. Atomic 10.81 26.98 69.72 114.82 204.37
Mass
Discovery 1808 1825 1875 1863 1861
Gay-Lussac, Oerstedt de Boisbaudran Reich, Crookes
Thenard, Davy Richter
Percentage on 0.001 7.7 1.6 * 10-3 1 * 10-5 5 * 10-5
earth
[Mass-%]
density [g/cm] 2.46 2.70 5.91 7.31 11.85
melting point 2250 660.3 29.8 156.6 303.5

[C] (sublimation)
boiling point 2330 2403 2070 1453
[C]
Electron 2.0 1.5 1.6 1.7 1.8
negativity
valence numbers -1,+1,+3, +1/+3 +1/+3 +1/+3 +1 (+3)
in compounds complex anions
Metallic/ Non-
metallic non-metallic metallic metallic metallic metallic
character
Electrical
isolator conductor conductor conductor conductor
conductivity
Acid/Basic
properties of acid amphoteric amphoteric amphoteric base
oxides
Stability of
valence states
+1
+3
Physiology not essential, not essential, - - toxic
non-toxic non-toxic
Electron configuration: sp1 (d10 ) need of loosing 3 electrons

for full saturation of electron shells
General Properties of Earth Metals
Valence states:
- + 1 and + 3 (+3 is favoured for B, Al, Ga and In, + 1 for Tl)

- complex anions of boron in compounds with electropositive elements

- covalent compounds
- formation of dimeric B2 H6 and of polymeric (AlH3)n
- GaH3, InH3, TlH3 were not found
- stability of hydrogen compounds:
B2H6 ( B H = +18 kJ/mol) < 1/n (AlH3)n (-11 kJ/mol)
Halogen compounds
- B: BHal 3, B2Hal4 and (BHal)n compounds

- Al: polymeric compounds
- Ga, In, Tl: XHal, X-XHal 4 and XHal 3 compounds
Binary compounds with chalkogenes
- X2 Y3, Ga, In, Tl forms additionally mono-chalkogenides X2 Y
Binary compounds with pnictogenes
- XY hard compounds, diamond-like structure, partially semiconductors
Acids/Bases
- B: H3BO3 acid properties

- Al, Ga, In: amphoteric X(OH) 3 compounds
- Tl: weak base Tl(OH) 3, strong base TlOH
Elementary Boron
Natural sources
- minerals: kernite Na2B4O7 4 H2O and borax Na2B4 O7 10 H2 O
Manufacture of the element

- amorphous boron (technical grade)
thermal reduction of B2 O3 with Mg
B2O3 + 3 Mg 2 B + 3 MgO + 533 kJ,
purification by treating with boiling diluted HCl
- crystallised boron of high purity
(1) reduction of boron halogenides (Cl, Br) with hydrogen
(1000 - 1400 C, W or Ta catalyst)
2 BHal 3 + 3 H2 2 B + 6 HHal
(2) thermal decomposition of BI3 at 800-1000 C
2 BI3 2 B + 3 I2 + 142 kJ
(3) thermal decomposition of B2H6
(600 - 800 C, BN, W or Ta catalyst)
B2H6 2 B+ 3 H2 + 36 kJ
Properties of the element

- properties between metals and non-metals
- one glass like amorphous and four crystalline modifications
- complex crystal structures with B12 icosa-hedrons as base unit,
partially including hetero atoms (e.g., B24C, B24N, B12P)
B12 icosa-hedron
- stable up to 400 C, reacts at >700 C with air, at >400 C with Cl 2,

at >700 C with S and at 900 C with N2
- stable in non-oxidising acids, in oxidising acids up to 250 C
- melting with alkali yields to alkali borates
- favoured oxidation state: +3
Boron Compounds (1)
Hydrogen compounds
- base element BH3 is not stable (electron shortage) and
has strong Lewis acid properties
- stabilisation
by intra-molecular adduct formation
(homologous rows Bn Hn+2 , BnHn+4 , BnHn+6 , BnHn+8 , BnHn+10),
as anions (e.g. BH4-, B3 H82-),
by formation of adducts
- toxic compounds with sickening odour, inflammable, short boranes are not stable in
water
- stability and acid strength increase with number of B atoms
(e.g. B6H10 - weak acid < B4H10 < B10H14 < B18H22 - strong acid),
- technical importance: B2H6 (made from 2 BF3 + NaH B2H6 + NaF)
for hydroboration reactions in organic chemistry
NaBH4 (made by Schlesinger process at
250-270 C
B(OMe)3 + 4 NaH NaBH4 + 3 NaOMe or
from borax, Na and H2
Na2B4 O7 7 SiO2 + 16 Na + 8 H2
4 NaBH4 + 7 Na2SiO3
Halogen compounds
- BHal 3, B2Hal4 and (BHal)n compounds

- BF3: - manufactured by treating borates with fluorspar and conc. H2SO4
B2O3 + 6 HF 2 BF3 + 3 H2O
- colourless, sticking gas, strong Lewis acid
- application: Friedels-Crafts catalyst, flowing agent
- HBF4:- manufactured by treating boron acid with hydrogen fluoride
H3BO3 + 4 HF HBF4 + 3 H2O
- use: strong acid for reactions catalysed by protons, galvanisation
- BCl 3: - manufacture: B2 O3 + 3 C + 3 Cl 2 2 BCl 3 + 3 CO
- colourless, smoking gas, high reactivity with water
(to H3BO3 + HCl)
- use: semiconductor industry, Friedels-Crafts catalyst,
high purity boron manufacture
Oxygen compounds and acids

- B2O3, HBO2 and H3BO3
- borax - Na2B4 O7 10 H2 O used for ceramics, enamels, glassware
- perborates - NaBO2 2 H2O used in detergents as leaching agent
Boron Compounds (2)

Boron nitride BN
- manufacture: B2O3 + 2 NH3 2 BN + 3 H2 O (800-1200 C) or
B2O3 + 3 C + N2 2 BN + 3 CO
- properties: highly inert material
- use: high temperature lubricant,
lining of rocket burning chambers, plasma burners and
nuclear reactors
Boron carbide B4C

- manufacture: B2O3 + 7 C B4C + 6 CO (at 2400 C) or
2 B2O3 + C + 6 Mg(4 Al) B4C + 6 MgO + 2 Al 2 O3
- properties: highly inert and hard material (similar than diamond)
- use: abrasive, manufacture of metal borides, armour plates,
neutron catcher in nuclear reactors
Elementary Aluminium
Natural sources
- minerals: corundum Al 2O3, hydrargillite (Al(OH) 3,
feldspar, clays, bauxite (alumosilicates), cryolithe Na3[AlF6 ]
Manufacture of the metal

- Bayer process for Al 2O3 manufacture
(1) treating of bauxite with 35-38 % NaOH
at 140-250 C and 5-7 bar for 6-8 hours
Al(OH) 3 + NaOH Na[Al(OH) 4]
separation from Fe(OH) 3
(2) precipitation by dilution (decrease of pH)
(3) calcinations to form Al 2 O3
- electrolysis of cryolyth (82 %)-alumina (18 %) mixture at 940-980 C
molten electrolyte carbon anode
isolation
liquid Al carbon cathode

- light silver-white and elastic metal
- high affinity to oxygen, but passivation
- not stable in acids (forming salts and H2) and
bases (forming aluminates and H2)
- favoured oxidation state: +3

- vehicles and aircraft
- containers and packaging
- construction industry
- office and household equipment
- iron and steel industry (alloys)
- aluminothermal welding (3 Fe 3O4 + 8 Al 4 Al 2O3 + 9 Fe + 3341 kJ)
- important compounds: Al 2O3, Al(OH) 3, Al 2(SO4)3, AlCl 3, NaAlO2, AlF3, NaAlF6,
spinells
Chapter 10
Alkaline Earth Metals

Group Beryllium Magnesium Calcium Strontium Barium Radium

Members Be Mg Ca Sr Ba Ra
Atom Number 4 12 20 38 56 88
Rel. Atomic 9.01 24.31 40.08 87.62 137.33 [226]
Mass radioactive
Discovery 1828 1809 1808 1790 1774 1898
Whler Davy Berzelius, Grawford Scheele Curie
Pontin
Percentage on 2.7 * 10-4 2.0 3.4 3.6 * 10-2 4 * 10-2 1 * 10-10
earth
[Mass-%]
melting point 1278 648.8 839 768 710 ~ 700
[C]
boiling point ~ 2500 1105 1482 1380 1537 ~ 1140
[C]
Density [g/cm] 1.85 1.74 1.54 2.63 3.65 unknown
at 25 C
and 1 bar
Electron 1.5 1.2 1.0 1.0 0.9 0.9
negativity
valence +2 +2 +2 +2 +2 +2
numbers in
compounds
Reducing/ moderate strong
Oxidation reducing reducing
Power agent agent
Metallic/ Non-
metallic silver-white or yellow-white metals
character
Acid/Basic
properties of amphoteric base
oxides
Physiology highly toxic essential essential not not
essential, essential,
not toxic but toxic
Electron configuration: s (d10 ) need of loosing 2 electrons

General properties: - occur in oxidation state +2

- non- noble metals, forming mostly exothermic compounds
with primary ionic character
(NOTE: Be forms covalent compounds!)
Chemical Properties of Alkaline Earth Metals

- monomeric XH2 compounds (except Be)
BeH2 ( BH ~ 0 kJ/mol, cannot be obtained from the elements
< MgH2 ( BH = -74 kJ/mol) < CaH2 (B H = -184 kJ/mol)
> SrH2 ( B H = -177 kJ/mol) > baH2 (B H = -172 kJ/mol)
- salt-like hydrides (except BeH2), stable under air
- reaction with water to hydroxides and H2
Halogen compounds
- Be: covalent halogen compounds (BeHal 2)n
with Lewis acid character
- higher elements: ionic salts XHal 2
Chalkogen compounds
- Be: BeY, stable in air and water
- higher elements: XY, stable in air, hydrolysis in water
(forming hydroxides and H2 Y)
Acides/Bases
- Be: Be(OH) 2, soluble in acid and base solutions
- higher elements: X(OH) 2, only soluble in acids, base reaction
Beryllium (1)
Natural sources
- rather rare element
- minerals: beryl - 3 BeO Al 2O3 6 SiO2,
bertrandite - 4 BeO 2 SiO2 H2O
- deposits in USA, Russia, Argentina and Brazil

Pre-processing:
- extraction of minerals with H2 SO4
- separation of aluminium salts with by precipitation with (NH4)2SO4
- precipitation of Be(OH) 2 with NH3
(1) - treating of Be(OH) 2 with NH4HF2 forming (NH4)2BeF4
- thermal decomposition of (NH4)2BeF4 at 900 1000 C
(NH4)2BeF4 BeF2 + 2 NH3 + 2 HF
(recycling of NH3 and HF)
- chemical reduction of BeF2 with Mg:
BeF2 + Mg Be + MgF2 at 1300 C
(2) - thermal conversion of Be(OH) 2 to BeO
- BeO + C + Cl 2 BeCl 2 + CO at 800 C
- purification of BeCl 2 by distillation at 485 C
- electrolysis of molten, water-free BeCl 2:
BeCl 2 Be + Cl 2 at 350 C
Properties
- grey, hard, brittle metal, stable under air up to 600 C and in water
- low density
- solved by diluted acids forming H2 (Be + 2 H+ Be2+ + H2),
passivation by oxidising acids
- reacts with electronegative elements only in the heat
- high toxicity of the pure metal (dust) and of Be compounds
Application
- limited by high price and high toxicity
- manufacturing of Be-Cu alloys for electrical equipment
(0.5 2.5 % Be increase of mechanical strength)
- moderator and reflector material in nuclear plants
- aerospace applications
Beryllium (2)
Chemistry
- formation of primarily covalent compounds
- electron shortage compounds with Lewis acid character ,
stabilisation by adduct formation and complexes
polymerisation by Lewis acid-base interactions
- amphoteric character of Be(OH) 2
Be(H2O) 42+ Be(OH) 2 Be(OH) 42-

soluble in precipitation soluble in
acid solutions in neutral solutions base solutions
- similarity to aluminium
covalent, polymeric hydrogen compounds (BeH2)x and (AlH3)y,
Lewis acid properties of halogenides,
amphoteric character of hydroxides
Magnesium (1)
Natural sources
- eighth most frequent element
- minerals (examples): magnesite MgCO3,
dolomite CaCO3 MgCO3,
carnallite KCl MgCl 2 6 H2 O,
kieserite MgSO4 H2O,
asbestos (silicates),
olivine [Mg, Fe)2SiO4]
- deposits in China, Russia, North Korea, Brazil, Australia
- remarkable amounts in seawater

(1) Pre-processing: thermal conversion of MgO
MgO + C + Cl 2 MgCl 2 + CO + 153 kJ/mol,
electrolysis of molten, water-free mixture of MgCl 2 (8 - 24 %)
and other alkali and alkaline earth metal chlorides,
MgCl 2 Mg + Cl 2 at 700 - 800 C, removal of molten Mg
(favoured process, 80 % of world Mg)
(2) thermal reduction of dolomite with ferrosilicon (vacuum, 1200 C)
2 (CaO MgO) + Si(Fe) 2 Mg + Ca2 SiO4 (slag) + Fe (slag)
Properties
- silver, middle-hard metal, oxidised under air and in water, but passivated
- low density
- solved by diluted acids forming H2 (Mg + 2 H + Mg2+ + H2),
passivation by oxidising acids
- strong reducing agent
- reacts with electronegative elements strongly exothermically (bright light) after
activation in the heat
- formation of compounds with intermediate ionic covalent character
- essential element
Application
- lightest construction metal
- manufacturing of Al-Mg alloys (< 10% Mg, casting alloys, wrought alloys) and Mg
based alloys with Al, Mn, Zn, Si, Be (Mg > 90 %, motor industry)
- reducing agent in organic and inorganic chemistry, Grignard reactions
- desulphurisation and deoxidification agent in iron and steel industry
- pyrotechnical applications
- manufacturing of metals (Be, Ti Kroll process)
Magnesium (2)
Important magnesium salts
Magnesium carbonate (MgCO3 ) - magnesite

- Manufacturing: mining of natural sources,
purification by gravitational separation, flotation or
magnetic separation;
synthetic salt produced by precipitation from Mg salts
Mg2+ + (NH4 )2 CO3 MgCO3 + 2 NH4 + or
by carbonating of MgO (e.g. obtained from dolomite)
MgO + 2 CO2 + H2 O Mg(HCO3 )2 in aq. solution
- Application: manufacturing of MgO, thermal insulating material,
filler in paper, plastics and rubber,
additive in table salt and in pharmaceuticals
Basic magnesium carbonate (Mg(OH)2 4 MgCO3 4 H2 O)

- Manufacturing: calcination of Mg(HCO3 )2
- Application: mild neutralisation agent,
used in medicine to neutralise antacid
Magnesium hydroxide (Mg(OH)2 )

- Manufacturing: precipitation from aqueous solutions of Mg salts
Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+
- Properties: low solubility in water, basic character,
soluble in acids and in NH4 + containing solutions
Magnesium oxide (MgO)

- Manufacturing: (1) calcination of magnesite or dolomite
at > 550 C
MgCO3 MgO + CO2
(2) precipitation from brines and seawater
with limestone
Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+,
calcination of Mg(OH)2
Mg(OH)2 MgO + H2 O
temperature: 600-900 C - caustic MgO,
1600-2000 C - sintered MgO,
melting at 2800-3000 C
fused/dead burnt MgO
- Application: caustic MgO fertilizers, animal feedstuff,
building materials, chemical and pharmaceutical
products, water treatment
sintered MgO refractory industry
(isolation of metallurgic kilns)
fused MgO insulating material in electrical heating
Magnesium (3)
Important magnesium salts (continuation)
Magnesium Chloride (MgCl2 )

- Manufacturing: (1) from brines and seawater
Dow Chemical process
- precipitation of Mg(OH)2 with lime
- Mg(OH)2 + Ca(OH)2 + 2 HC l + 2 H2 SO4
MgCl2 + CaSO4 + 4 H2O
- evaporation at 200 C MgCl2 2 H2 O
- evaporation at 300 C MgCl2
(2) from Mg carbonate or oxide (burnt magnesite)
Norsk-Hydro process (magnesite + seawater)
2 MgO + 2 Cl2 + (2) C 2 MgCl2 + CO2 (or CO)
(3) MPLC process
MgO + Cl2 + CO 2 MgCl2 + CO2
(4) dehydration of hexahydrate
- Application: electrochemical manufacture of Mg (80 %),
granulation of fertilizers, as a dust binder,
in oil and sugar industry,
mixtures of MgO and MgCl2 used for production
of Sorel cement and lightweight building panels
Magnesium sulphate (MgSO4 )

- Manufacturing: (1) mining of kieserite or from brines
(2) byproduct of K salt processing
(3) reacting of carbonates or seawater with H2 SO4
- Application: fertilizer (80 %), manufacture of K2 SO4 , Na2 SO4 and
K-Mg sulphate (potash magnesia),
textile and cellulose industries,
production of building materials, refractory materials,
animal feedstuffs and motor oil additives
Calcium, Strontium, Barium and Radium
Common chemical properties
- metals are oxidised in the presence of air and water

- solved by diluted acids forming H2
- strong exothermic reactions with electronegative elements after thermal activation
- formation of primarily ionic compounds with cations M2+
- low solubility of sulphates, fluorides, carbonates, silicates and phosphates (but high
solubility of hydrogen carbonates and
monohydrogen/dihydrogen phosphates)
- low solubility of hydroxides, basic reaction of the solution
Calcium
Natural sources
- 5th most frequent element, widely distributed all over the world
- minerals: limestone CaCO3,
dolomite CaCO3 MgCO3
gypsum CaSO4 2 H2O, anhydrite CaSO4,
apatite Ca5(PO4)3F,

- thermal reduction with aluminium (vacuum, 1200 C)
6 CaO + 2 Al 3 CaO Al 2O3 (cement slag) + 3 Ca (g)
- electrochemical processes are no longer operated

- silver-white metal with low density

- reducing agent in manufacturing of Zr, Th, U and rare earth metals
- refining agent in metallurgy
- maintenance-free batteries (Pb/Ca alloys)
- manufacturing of SmCo 5 magnetic materials
Limestone and Construction Materials
Calcium carbonate (CaCO3) - limestone

- manufacturing: open cast mining,
synthetic fine-grained CaCO3 by carbonating
milk of lime (pigments for paint and paper industry)
Calcium sulphate (gypsum CaSO4 2 H2O, anhydrite CaSO4)

- manufacturing: open cast mining,
by-product of manufacture of H3PO4 and of HF,
by-product from waste gas desulphurisation
The limestone cycle in manufacture of construction materials
(2)
Ca(OH)2 (3)
CaCO 3 (1) CaO CaCO 3
(slake lime/
(limestone) (quicklime) (limestone)
lime hydrate)
(1) calcinations of limestone at 1000 1200 C

178.4 kJ/mol + CaCO3 CaO + CO2
(2) slaking of CaO = slow addition of water
CaO + H2 O Ca(OH)2 + 65.2 kJ/mol
(3) use of slake lime in construction,
binding of slake lime with atmospheric carbon dioxide
Ca(OH)2 + CO2 CaCO 3 + H2O
cement = 3 CaO SiO 2 ,

obtained by thermal treating
of a mixture of CaO, SiO 2 and some additives
(Fe2 O3 , Al2 O3 ) at 1450 C
lime mortar = mixture of slake lime and sand
gypsum mortar = suspension of anhydrite, hardening by local
solution and re-crystallisation
Other applications of limestone, quicklime and slake lime

limestone: - fertilizer
- steel industry
quicklime and slake lime: - metallurgy (removal of P and S)
- water and effluent treatment
- chemicals
(carbides, cyanamides,
Na2 CO3 Solvay process)
- agriculture and sugar industry
- refractory materials
- flue gas desulphurisation
Other Calcium Compounds
Calcium carbide (CaC2)
- manufacturing: reacting highly purified CaO with coke

in an electrical furnace at 2000 2200 C
464 kJ/mol + CaO + 3 C CaC2 + CO
- application: - formation of acetylene
CaC2 + 2 H2 O C2H2 + Ca(OH) 2 (exothermic !),
widely applied in welding and
in manufacture of special cast iron,
- formation of calcium cyan amide (CaCN2)
- desuphurisation and deoxidation
of raw iron and steel
Calcium cyan amide (CaCN2) - nitro-lime
- manufacturing: CaC2 + N2 CaCN2 + C + 296 kJ/mol (700900 C)

- application: - long-time NH3 fertilizer
(CaCN2 + 3 H2O CaCO3 + 2 NH3 + 91.3 kJ/mol)
- herbicide
- manufacturing of organic chemicals
Calcium fluoride (CaF2)
- manufacturing: mining and purification of fluorspar

- application: - manufacturing of HF
- enamel industry
- optical prisms and lenses (high UV transmission)
Calcium fluoride (CaCl 2)
- manufacturing: waste product from many processes

- soda manufacturing (Solvay process)
CaCO3 + 2 NaCl Na2 CO3 + CaCl 2
- propylene oxide from chlorhydrin
- treating waste HCl with limestone
vaccum and atmospheric pressure evaporation,
traded as 30 45 % solution or as 75 % flakes
- application: - dust binder (road re-construction, mines)
- cooling, defrosting and antifreeze agent
(e.g. road de-icing in strong winters main use)
- drying agent (laboratory scale)
available amount exceeds demand
Strontium and its Compounds
Natural sources
- minerals: celestine SrSO4,
strontianite SrCO3
- deposits in Mexico, Spain, Turkey and Great Britain

- elementary metal is not used in technical scale
- laboratory scale: chemical and electrochemical reaction

- light gold-yellow metal with low density
- vaporised Sr emits red light
Strontium compounds
SrCO3: - manufacturing: mining
- application: manufacture of special glasses
(CRT-screen glassware for colour TV
and computer monitors),
magnetic materials,
pigments and fillers,
electrolytic Zn manufacture
(precipitation of Pb and Cd salts)
Sr(NO3)2: - manufacturing: SrCO3 + 2 HNO3

Sr(NO3)2 + CO2 + H2O
- application: fireworks
Barium and its Compounds
Natural sources
- minerals: heavy spar/ barite BaSO4,
(witerite BaCO3, not mined)
- deposits in China, USA, India, Russia

- elementary metal is only used in special applications
(getter material in the manufacture of valves)
- laboratory scale: chemical and electrochemical reaction

- gold-yellow metal with low density
- vaporised Ba emits green light
Barium compounds
BaSO4: - manufacturing: (1) mining
(2) oxidation of BaS with Na2 SO4
- application: drilling-mud for oil and gas exploration
(90 % of mined BaSO4),
white pigment (manufacture of paper, paint,
rubber and plastics)
BaCO3: - manufacturing: 3 step process

(1) BaSO4 + 4 C 4 BaS + 4 CO
(rotary kiln, 1200 C)
(2) BaS + CO2 + H 2O BaCO3 + H2S or
BaS + Na2CO3 BaCO3 + Na2S
(in aq. solution)
- application: tile and ceramic industry
(preventing bleading of Na and Ca sulphates),
special ceramics as Ba ferrite and Ba titanate,
glass industry producing of special optical
glassware and CRT-screens,
manufacturing of photographic papers
BaO2: - manufacturing: glowing of BaCO3 and coke

BaCO3 + C BaO + 2 CO,
thermal oxidation of BaO at 500-600 C
2 BaO + O2 2 BaO2
- application: igniting agent
Ba(NO3)2: manufacturing: BaCO3 + 2 HNO3 Ba(NO3)2 + CO2 + H2O

- application: fireworks
Chapter 11
Alkali Metals
Group Lithium Sodium Potassium Rubidium Caesium Francium

Members (Li) (Na) (K) (Rb) (Cs) (Fr)
Atom Number 3 11 19 37 55 87
Rel. Atomic 6.94 22.99 39.10 85.47 132.91 [223]
Mass (radio-
active)
Discovery 1817/18, 1803, 1807, 1861/62, 1860, 1939, Perey
Arfevedson, Davy Davy Bunsen, Bunsen,
Davy Kirchhoff Kirchhoff
Percentage on 2.0 10-3 2.7 2.4 9.0 10-3 3.0 10-4 1.3 10-21
earth
[Mass-%]
melting point 180.5 97.8 63.6 38.9 28.4 ~ 27
[C]
boiling point 1347 881.3 753.8 688.0 678 ~ 660
[C]
Density [g/cm] 0.53 0.97 0.86 1.5 1.9 unknown
at 25 C
and 1 bar
state at 25 C malleable
and 1 bar malleable silver metals golden
metal
Electron 1.0 0.9 0.8 0.8 0.7 0.7
negativity
valence +1 +1 +1 +1 +1 +1
numbers in
compounds
Reducing/
Oxidation strong reducing agents
Power
Metallic/ Non-
metallic typical metals
character
Acid/Basic
properties of basic oxides and hydroxides
oxides
Electron configuration: s1 (d10 ) need of loosing 1 electron

General Properties of Alkali Metals (1)
Manufacture of metals
- electroylsis of molten, water-free salts (Downs process):
2 LiCl 2 Li + Cl 2 at 610 C
2 NaCl 2 Na + Cl 2 at 600 C
- chemical reduction: KCl + Na K + NaCl (850 C)
2 RbOH + Mg or Ca
Mg(OH) 2 or Ca(OH) 2 + Rb
Cs 2Cr2O7 + 2 Zr
2 Cs + 2 ZrO2 + Cr 2O3
(500 C , high vacuum)
Physical properties
- malleable metals with low melting and boiling temperatures
- low density (Li, Na and K less than water)
- coloured vapours at higher temperatures
(consisting of atoms and molecules M2)
(Li: red, Na: yellow, K: violet, Rb: red, Cs: blue)
Chemical propertes
- strong reducing agents

- metals will be oxidised under air atmosphere even at room temperature (traces of
humidity are necessarily)
- occur in nature only as salts
- oxidation number in compounds: +1,
- similarity between Li and Mg (e.g. solubility of salts)
- formation of binary compounds with all non-metallic (electronegative) elements
(e.g. H hydrides, C carbides, N nitrides, S suphides)
- Na and K are essentially for biological processes
Hydrogen compounds
- stable exothermic ionic hydrids MH with salt-like properties,

stable up to 360 C (RbH) - 970 C (LiH)
- formation from the elements M + 1/2 H2 MH at temperatures:
LiH 600-700 C, KH, RbH and CsH 350 C, NaH 250-300 C)
- formation enthalpies:
LiH 93.2 kJ/mol, NaH 57 KJ/mol, KH 56 kJ/mol, RbH 55 kJ/mol,
CsH 50 kJ/mol)
- strong reducing agents
- reactions:
2 MH + O2 M2O + H2O (hydrides are flammable)
MH + H2O MOH + H2
MH + NH3 MNH2 (amides) + H2
MH + Hal 2 MHal + HHal
- Application
LiH: hydrogenation agent in organic and inorganic chemistry
NaH: base compound in organic reactions (Claisen condensation,
aldol additions, alkylation and acylation reactions,
reducing agent in inorganic chemistry,
synthesis of hydride compounds,
manufacturing of pure metals (Hydrimet process)
Hydroxides
- Synthesis: (1) hydroxides are made by electrolysis of chlorides

2 M+ +2 Cl - + 2 H2O 2 MOH + 1/2 H2 + 1/2 Cl 2
(NaOH/KOH: mercury and membrane process,
diaphragm process only for NaOH)
see chlorine alkali electrolysis, chapter 6)
(2) caustification of carbonates old industrial process
Na2CO3 + Ca(OH) 2 2 NaOH + CaCO3
only for NaOH
- Properties: strong basic character,
no decomposition to oxides in the heat
- Application: NaOH - widely used basic substance ,
e.g. for manufacture of soaps, dye stuffs and cellulose,
- for synthesis of a lot of chemicals,
for purification of fats, oils and petroleum
KOH - manufacture of soaps, potash, phosphates and
other potassium compounds
Chalkogen compounds (general)
- formation of compounds M2 Y (chalkogenides) with partially covalent character,

M2 Yn>1 (perchalkogenides) and M>2 O (suboxids)
- properties of sulphides chapter 7
Oxides, suboxides, peroxides and ozonides
Oxides M2O Peroxides M2O2 Hyperoxides MO2 Ozonides MO3
Li Li2O2 Li2O24
Na Na2O1 Na2O22 NaO23 NaO35
K K2O6 K2O21 KO22 KO35
Rb Rb2O6 Rb2O21 RbO22 RbO35
Cs Cs 2O6 Cs 2O21 CsO22 CsO35
Manufacture:
1 from the elements under careful oxygen and
temperature control
2 combustion of M in under oxygen excess
3 formation under large oxygen excess and high pressure
4 reaction of MOH with H2 O2 and thermal decomposition
5 oxidation of hyperoxides or of hydroxides with ozone
at temperatures < 0 C
(MO2 + O3 MO3 + O2,
3 MOH + 2 O3 2 MO3 + MOH H2O + 1/2 O2),
6 com-proportionation reaction M2 O2 + M 2 M2 O or
2 MNO3 + 10 M 6 M2O + N2)
Properties:
- oxides are stable up to 500 C,
peroxides are stable up to 500 - 600 C (Li 2O2 up to 200 C)
hyperoxides are stable (except RbO2 only up to 450 C)
decomposition of ozonides at room temperature
- reaction with water
peroxides: decomposition to H2O2, O2 and OH-
hyperoxides: 2 O2- + 2 H2O O2 + H 2O2 + 2 OH-
ozonides: 4 O3- + 2 H2O 5 O2 + 4 OH-
Application: Na2O2 leaching agent
Li2O2, Na2O2, KO2 oxygen source and CO2 absorber in respirators
(e.g. 4 KO2 + 2 CO2 K2 CO3 + 3 O2)
General properties of salts

- oxidation number of alkali metals +1
- mostly ionic character (depending on the nature of the anion)
- high thermal stability (depending on the nature of the anion), high melting and
boiling points
- high solubility in water (mostly kg/l, except some Li salts and perchlorates of K,
Rb, Cs)
dissociation into solvatisated cations and anions (solutions conduct electricity)
- NH3 acts partially as a pseudo alkaline metal
Halogen compounds
- stable ionic halogenides MHal with salt-like properties

- formation from the elements in partially strong exothermic reactions
- primary natural sources of alkali metals and halogens
Lithium and Its Salts
Elementary lithium
- manufacturing: electrolysis of molten LiCl/KCl mixture at 400-460 C

- application: - synthesis of Li hydride and Li amide
- synthesis of organic lithium compounds
(reducing age nt, polymerisation catalysts)
- manufacture of extremely light
and strong Al -Li alloys (2 - 3 % Li)
for space applications
- batteries
Lithium carbonate (Li 2CO3)
- manufacturing: precipitation from soluble Li salts

2 Li + + CO32- Li2CO3
- application: - agent for decreasing melting temperature
in aluminium manufacture
- flux in glass, enamel and ceramic industries
- medicine (psychiatry)
- manufacture of fire-resistant glassware
Lithium hydroxide (LiOH)
- manufacturing: Li2CO3 + Ca(OH) 2 CaCO3 + 2 LiOH

- application: - manufacturing of Li soaps and greases
Lithium hydride (LiH)
- manufacturing: 2 Li + H2 2 LiH at 700 C

- application: - drying agent
- hydrogen storage
- reducing agent in organic chemistry (LiAlH4, LiBH3)
Lithium nitrate (LiNO3)
- manufacturing: Li2CO3 + 2 HNO3 2 LiNO3 + CO2 + H2O

in aqueous solution
- application: red fireworks
Manufacture of Soda Ash - The Solvay Process
Process steps
(1) preparation of a concentrated NaCl solution
(2) saturation of the solution with NH3 under cooling
(3) saturation of the solution with CO2 at 50 C

NH3 + CO2 + H2O NH4+ + HCO3-
NH4+ + HCO3- + Na + + Cl - NaHCO3 + NH4+ + Cl -
(4) thermal decomposition of NaHCO3 at 170 180 C

2 NaHCO3 Na2CO3 + H2O + CO2 (recycling to step 3)
(5) producing of additional CO2 by calcination of limestone at 900 C

CaCO3 CaO + CO2
(6) regeneration of ammonia

2 NH4+ + 2 Cl - + CaO 2 NH3 + Ca2+ 2 Cl - + H2O
(CaCl 2 cannot used in further processes and is an waste
difficult to depose)
Summary:
2 NaCl + CaCO3 Na2CO3 + CaCl 2
(occurs in aqueous solution in the opposite direction)
Sodium and its Salts
Salt Manufacture Application
elementary - electrolysis of molten NaCl (modified - reducing agent, catalyst in organic

Na Downs process) chemistry
- manufacture of NaH, NaBH4 , Na2 O2
etc.
- coolant in nuclear reactors
(fast breeders)- sodium-sulphur
batteries
NaCl - mining or underground solving of - starting material for all other inorganic
rock salt deposits Na compounds
(in Germany - Stafurt/Zielitz, Austria, (e.g. Na2 CO3 , NaOH, Na2 SO4 ,
Spain, USA, Russia) and purification Na2 B4 O7 , Na2 SiO 3 )
by flotation, - raw material for chlorine alkali
- vaporising, freezing or electrodialysis electrolysis
of sea water - food industry
Na2 CO3 - mining of trona deposits (USA), - glass industry
(soda ash) purification by solving, evaporating and - synthesis of inorganic Na salts
calcination - pulp and paper industry
- Solvay process (Europe) - soap and detergent production
2 NaCl + CaCO3 Na2 CO3 + CaCl2
NaHCO3 - Na2 CO3 +H2O + CO2 2 NaHCO3 - food industry (baking powder
(high purity) production)
- animal feedstuff
- rubber, chemical, pharmaceutical,
textile, leather and paper industries
NaNO3 - mining of natural deposits (Chile) - fertilizer
- Na2 CO3 +2 HNO3 2 NaNO3 + H2O
+ CO2
Na2 SO4 - mining of natural deposits (Russia, - pulp and paper industry
(Glaubers USA, Canada) - additive in detergents
salt) - 2 NaCl + H2 SO4 Na2 SO4 + HCl - glass industry
(800 C) - chemical industry
- 2 NaCl + MgSO4 Na2 SO4 + MgCl2
(in aq. solutions)
(deep temperature precipitation of
Na2 SO4 )
NaHSO4 - 2 NaSO 4 + H2 SO4 2 NaHSO4 - cleaning agents
- byproduct of CrO 3 manufacture - flux
(Na2 Cr2O7 + 2 H2SO4 2 CrO3 + 2
NaHSO4 + H2 O)
NaB4 O7 - extraction from borate minerals - glass, enamel, china and ceramic
(borax) (dissolving in H2 O, followed by industries
selective crystallisation at 60 C) - manufacture of perborates for
- dehydratisation by calcination at 350- detergents
400 C - flux, falme and corrosion inhibitor
Potassium and its Salts
Salt Manufacture Application
elementary K - KCl + Na K + NaCl (760-880 C, - only limited importance

favoured process) - manufacture of KO2
- 2 KF + CaC 2 CaF2 + 2 C + 2 K - manufacture of low melting Na-K
(1000-1100 C) alloys (reducing and drying agent, heat
transfer medium)
KCl - mining or underground solving of salt - starting material for all other
deposits (deposits in Germany - inorganic K compounds
Stafurt/Zielitz, Hanover, Werra/Fulda - production of K containing fertilizers
region - France, Canada, USA, Russia) (KCl, K2 SO4 , KNO 3 )
and purification by flotation - metallurgy, enamel industry,
manufacture of soaps
- manufacture of special IR transparent
optical glassware
KBr - halogenation of potash with Fe(II, III)- - photographic industry
bromide - manufacture of special IR transparent
4 K2 CO3 + Fe3 Br8 8 KBr + Fe3 O4 + optical glassware
4 CO2
- bromation of potash
3 K2 CO3 + 3 Br2 5 KBr + KBrO 3 + 3
CO2
KI - halogenation of potash with Fe(II, III)- - photographic industry
iodide - manufacture of special IR transparent
4 K2 CO3 + Fe3 I8 8 KI + Fe3O4 + 4 optical glassware
CO2
- reduction of KIO 3
K2 CO3 - carbonation of KOH - glass and enamel industry, pigment
(potash) KOH + CO2 K2 CO3 + H2 O manufacture
(precipitation, calcination at 250-350 - manufacturing of soaps and detergents
C) - food industry
- starting material for many inorganic
and organic K compounds
KNO3 - KCl + NaNO3 NaCl + KNO3 - fertilizer
(saltpetre) - 2 KCl + 2 HNO3 + 1/2 O2 2 KNO3 - component of gun powder
+ Cl2 + H2 O
K2 SO4 - 2 KCl + H2 SO4 K2 SO4 + HCl (700 - fertilizer (trading of K2 SO4 and K2 SO4
C) MgSO4 )
- 2 step process in aq. solutions:
(1) 2 KCl + 2 MgSO4 K2 SO4
MgSO4 + MgCl2
(2) K2 SO4 MgSO4 + 2 KCl 2 K2 SO4
+ 2 MgCl2

Inorganic Chemistry Course Chapter 1: Elements, Compounds, Atoms and Electron Orbitals

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Inorganic Chemistry Course Chapter 1: Elements, Compounds, Atoms and Electron Orbitals

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Course on Inorganic Chemistry

Elements and Compounds,

Solutions Pure substances

Antiquity/Middle Ages - The Four Elements

1642 Jungius - Pioneer works on the present-day theory of

1869 - Proposal of the Periodic Table of Elements by

Number of elements discovered

Antiquity 19th century

Earths crust Human biomass

1808 - Hypothesis of atoms by Dalton

Protons Neutrons Electrons

contain the mass responsible for chemical

absolute mass unit u [amu] = 1/12 * m(12C)

Relative masses of atoms (Ar) and molecules (Mr)

Ar or Mr = (mA or mM)/u (IUPAC 1961)

Molar masses M [g/mol]

Numbers of Ar or Mr and M are identically!

Radius of atoms: 0.33 * 10-10 m

Other important constants

Schrdinger equation (1926)

The Uncertainty Principle by Heisenberg (1927)

Electron orbitals as the solutions of the Schrdinger equation:

rooms of highest probability (90 % or more) of finding the electron

s orbital px orbital py orbital pz orbital

dxy orbital dxz orbital dvz orbital

The three fundamental properties of electrons: mass, charge, spin

The Pauli principle (Wolfgang Pauli, 1924):

Every electron orbital can be characterised by a set of quantum numbers

l orbital angular momentum quantum number (subshell number)

m orbital magnetic quantum number

s spin magnetic quantum number

- RESULT: Periodicity of number of valence electrons

Radius of orbitals of neutral atoms

contraction with increased proton number for each shell

First and second ionisation potential

Atom Absorption Spectroscopy (AAS)/ Term scheme for sodium (Na)

using of outer electron transitions

X-ray Flourescence Spectrometry (XFS)

using of inner electron transitions

(1) absorption of primary X-ray

electron energy [eV]

Main group elements

IIIb IVb Vb VIb VIIb VIIIb Ib IIb

s block d block p block

Ia VIIIa, Ib VIIIb = group numbers

name of the element colour = metallic or non-metallic character or

1869- Mendelejew Proposal of the Periodic Table of Elements,

1886 Winkler Discovery of Germanium in a silver containing

Properties Properties found Present State

relative atom mass 72 72.32 72.61

1789 Lavoisier Theory of radicals

1807 Davy Chemical bonds as electrochemical attraction,

1852 Frankland Definition of valence as the ability of a given atom to

1857/58 Kekul Multiple carbon bonds in organic substances,

1861 Butlerov Theory of chemical structures,

1874 vant Hoff Stereochemistry

1910 Stark Coherence between valency and outer electrons

1916-19 Lewis Octet rule (noble gas shells),

1927-29 Hund Mulliken Quantum mechanical LCAO-MO-theory

1927-31 Heitler, Quantum mechanical valence bond theory

1931 Pauling Hybridisation

CH4 NH3 H2O

allow to predict reactions (G = ZF)