Professional Documents
Culture Documents
by Frank Klose
Chapter 1
Substances
Heterogeneous Homogeneous
substances substances
Compounds Elements
The Discovery of the Chemical Elements
200 175
150
115
100 82
50 32
12 14 15
0
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
Atom
Core Shell
positive no negative
charged charge charged
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
H = E
H Hamilton operator
E Energy of the electron
- Wave functio n
x * p h/4
x uncertainty of the position of the electron
p - uncertainty of the impulse of the electron
h Planck constant
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
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)
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.
electron
core
2nd shell
1st shell
electron
core
3rd shell
2nd shell
1st shell
Electron affinity
Atomic Spectroscopy
Principle of spectroscopy
Excitation Relaxation,
(specific or non-specific), Emission
absorption of specific radiation
Lanthanides
Actinides
atomic number Z
(= number of protons)
rel. atomic mass
(= molecular mass)
electron
negativity
chemical symbol
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).
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
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
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
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
- number of bonds =
number of bonded MO - number of anti-bonded MO
Quantum Mechanical Concepts of Molecular Bonds
2. Theory of Valence Bonds (VB Theory)
H + H H-H H? H? H? H?
Ethylene Acetylene
(C-C double bonds) (C-C triple bonds)
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
ability to be oxidised
electron affinity,
Lanthanides
ionisation energy,
non-metallic character,
acid strenght of oxides, Actinides
oxidation state (valency)
Course on Inorganic Chemistry
Chapter 2
Chemical Reactions
The Chemical Equilibrium
If back reaction
C + D
A + B with r-1 = k-1 * [C] * [D]
k 1
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 )
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
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
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
membrane
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)
a) metals
acid solution basic solution
- valid for water and other protical solvents (e.g. liquid NH3)
Principle of hard and soft acids and bases (HSAB principle - by Pearson 1963)
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
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).
Literature/References for Figures
Chapter 3
Noble Gases
Overview About the Group
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.)
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)
Xenon(VI)-oxide (XeO 3 )
Xenon(VIII)-oxide (XeO 4 )
Oxiflouride Compounds
Chapter 4
Hydrogen
Overview
Hydrogen isotopes
Electron configuration: s1
needs to spent or to accept one electron
occurs in elementary form as diatomic H2
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
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)
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
- strong reducing agents, industrial use for manufacturing pure elements (e.g. LiH,
NaH, CaH2)
General:
- formed with transition metals and the metals of the III.-VI. main group
Preparation:
solution hydride
phase phase
hydrogen pressure
mixed phase
(solution + hydride)
plateau region
Stability:
- hydrogen atoms occupy lattice gaps, they can move inside the gap
- 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:
period period
Reactions
- protonation/deprotonation (Va-VIIIa group elements)
H+ + H2O H3O+
NH3 + H3O+ NH4+ + H2O
NH3 NH2- + H+
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
Chapter 5
Halogens
Overview About the Group
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)
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
Manufacturing in industry:
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
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 -
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
Natural Sources:
seawater (main source)
residual solutions from potash (K2CO3) industry
Manufacturing in 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
Manufacturing in industry:
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
Manufacturing in industry:
Conversion of fluorspar CaF 2 (Bayer Process)
CaF 2 + H2SO4 CaSO4 + 2 HF (200-250 C)
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
Manufacturing in industry:
(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
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:
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)
Nomenclature:
HXO hypohalogenous acid XO- - hypohalogenite
HXO2 halogenous acid XO2- - halogenite
HXO3 halogenic acid XO3- - halogenate
HXO4 perhalogenic acid XO4- - perhalogenate
Acids:
Base Anions:
(8) Werner Bchner, Reinhard Schliebs, Gerhard Winter, Karl Heinz Bschel,
Industrial Inorganic Chemistry,
VCH Verlagsgesellschaft Weinheim, 1989
Pseudo Halogenes
Atom Groups
Chapter 6
Chalkogens
(Oxygen Group)
Overview About the Group
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
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)
UV radiation
emissions
hydrocarbons, CO
emissions
Chapman cycle
O3 + X O2 + OX
OX+ O X + O2
O3 + O X
2 2
(X = NO, H, OH natural, Cl, Br anthropogenic)
Peroxides
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
Technical application of H2 O2
- leaching agent
- production of perborates for detergents: NaBO2 + H2O2 NaBO3 + H2 O
300
250
200
150
100
50
0
1960- 1984 1985 1986 1987
1970
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)
steam
sulphur containing
limestone
molten
sulphur
rock
Sulphur (2)
Sulphur modifications
melting boiling
point point
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
- 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
1 1st tray
SO3 decomposition catalyst (60 % conversion)
1st heat
exchanger
2nd tray
catalyst (90 % conversion)
SO3 yield
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
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
- semi- metallic 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
water molecule
104.9
Physical properties
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
Course on Inorganic Chemistry
Chapter 7
Pnictogens
(Nitrogen Group)
Overview About the Group
Valency states:
- 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)
- 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
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
Starting materials
- air (nitrogen and oxygen)
- water
- natural gas, oil or coke
steam partial
rectification gasification
reforming oxidation
nitrogen oxygen
absorption of CO and H 2S
ammonia synthesis
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)
Industrial Ammonia Synthesis
2. Pre-Processing Steps (2)
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)
pressure
resistent
outer tube
catalytic
contact
heat
exchanger
tube
Process conditions
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
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)
NO
air +
ammonia
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
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
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
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
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
pH
- 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)
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
Course on Inorganic Chemistry
Chapter 8
Carbon Group
Overview About the Group
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)
Halogen compounds
- C and Si: substitution of hydrogen atoms by halogens
- Ge, Sn and Pb: XHal 2 and XHal 4 compounds
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
Fullarene-60
Hydrocarbons and Halogenated Hydrocarbons
straight and branched aliphatic compounds with only single C-C bonds
(saturated hydrocarbons)
ethylene C 2H4 propylene C3H6 butadiene C4H6 acetylene C2H2 propine C3H4
- 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
- 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
- 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)
Industrial Carbon Oxide Chemistry (2)
Synthesis Gas
temperature
Synthesis Gas
- Application:
ammonia
urea resins
synthesis
oxidation
formaldehyde polyols
paraffins
acetates
coal olefins
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
Natural sources
- second most common elements
- occurs only in compounds
- minerals: quartz sand (SiO2), silicates
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)
cyclopentasilane cyclohexasilane
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
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
Manufacturing:
Precursors:
- (chloro)methylsilanes
- (chloro)phenylsilanes
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
Silicone Rubbers
- crosslinked polysiloxanes
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)
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
Tin 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
Natural sources
- occurs primarily in form of sulphidic ores
Lead compounds
- typical reactions and compounds of IVa group elements
- oxidation state + 2 is favoured compared to + 4
(strong oxidation agent)
- amphoteric (predominantly acid) character of hydroxides
Chapter 9
Earth Metals
(Boron Group)
Overview About the Group
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
Valence states:
Halogen compounds
Acids/Bases
Natural sources
- occurs only in compounds
- minerals: kernite Na2B4O7 4 H2O and borax Na2B4 O7 10 H2 O
B12 icosa-hedron
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
Natural sources
- occurs only in compounds
- minerals: corundum Al 2O3, hydrargillite (Al(OH) 3,
feldspar, clays, bauxite (alumosilicates), cryolithe Na3[AlF6 ]
isolation
Chapter 10
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
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
- 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
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)
Magnesium (3)
Important magnesium salts (continuation)
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,
(2)
Ca(OH)2 (3)
CaCO 3 (1) CaO CaCO 3
(slake lime/
(limestone) (quicklime) (limestone)
lime hydrate)
Natural sources
- minerals: celestine SrSO4,
strontianite SrCO3
- deposits in Mexico, Spain, Turkey and Great Britain
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)
Natural sources
- minerals: heavy spar/ barite BaSO4,
(witerite BaCO3, not mined)
- deposits in China, USA, India, Russia
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)
Chapter 11
Alkali Metals
Overview About the Group
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
Hydrogen compounds
Hydroxides
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 Alkali Metals (4)
Halogen compounds
Elementary lithium
Process steps
Summary:
2 NaCl + CaCO3 Na2CO3 + CaCl 2
(occurs in aqueous solution in the opposite direction)
Sodium and its Salts