Humboldt-Universität zu Berlin - Faculty of Mathematics and Natural Sciences - Department of Chemistry

Rare Gases

Their position in the periodic table; occurrence and isolation; physical properties, chemical properties. Chemical compounds of rare gases: halogenides and related compounds; oxo compounds of xenon; syntheses and chemical properties; structure and bonding in rare gas compounds.

Hydrogen and its compounds

Hydrogen: occurrence; preparation in the laboratory; technical processes for hydrogen production: electrolysis of water; from fossile sources (natural gas, oil, coal); cracking of hydrocarbons; steam reforming. — Physical properties: isotopes, isotope effects; atomic hydrogen, hydrogen in statu nascendi; ortho- and para-hydrogen. — Chemical properties: homolytic and heterolytic bond scission;redox behaviour; hydrogen-oxygen reaction: radical chain mechanism; catalytic hydrogenations. — Uses of hydrogen: synthesis of ammonia; hydrogenation of carbon compounds (gasoline); hardening of fats; hydrogen as a rocket fuel.

Binary hydrogen compounds: covalent, ionogenic, metallic and complex hydrides; transi-tion metal hydrides; hydrides of main group elements (synthesis, stability, properties, uses)

Alkali metals

Historic aspects (discovery, isolation). Occurrence, preparation; physical and chemical properties: molten salt electrolysis, tendencies in their atomic and ionic radii, ionization potentials, reactivity vs. oxygen, halogenes and water; solutions of alkali metals in liquid ammonia.Uses of alkali metals:

Lithium: alloys; metallurgy; fatty acid salts of Li in lubricants; organo-lithium compounds. Lithium batteries.

Sodium: coolant in nuclear reactors, discharge lamps; reducing agent; Na₂O₂ , NaNH₂ (synthesis of indigo): NaCN in cyanide process; NaH and NaBH₄; sodium chloride (rock salt, chlorine production); NaOH, Na₂SO₄, Na₂CO₃ (glass, detergents, textiles, cellulose, paper); sodium bicarbonate (Solvay process, flue-gas desulfurization); Na₂O₂ (synthesis, uses)

Potassium: metallic potassium (uses and preparation); alloys of potassium and sodium. Important compounds: KCl (fertilizer, production of KOH, K ₂CO₃); KNO₃ (fertilizer, black powder, pyrotechnics); potash K₂CO₃ (detergents, glass, china, pigments). Analysis of alkali metals: flame spectroscopy, sparingly soluble salts of alkalies.

Halogenes

Historic aspects (discovery, isolation). Occurrence, preparation; physical and chemical properties. Fluorine (electrolysis of K/HF-melts); Chlorine (electrolysis of aqueous NaCl; Deacon process); Bromine (oxidation of bromide from carnallite brines and seawater using Cl₂). Iodine (reduction of iodate from Chile salpeter)

Uses of halogenes: Fluorine: preparation of inorganic and organic fluorine compounds; UF₆, SF₆, surface fluorination of polymers, PTFE. Chlorine: oxidant, bleach, disinfecting agent; preparation of inorganic and organic chlorine compounds, PVC. Bromine:oxidant, bleach, disinfecting agent; preparation of inorganic and organic bromine compounds (flame retardants). Iodine: disinfecting agent, van Arkel de-Boer process, radiotherapy.

Halogene compounds, preparation and properties:

hydrogen halides: HF: from CaF₂ and H₂SO₄; HCl: from the elements, Leblanc process; byproduct of chlorination and halogene exchange reactions; HBr: from the elements (technically), lab: Br₂/tetraline; P/Br₂/H₂O; HI: from the elements; lab: I₂/P/H₂O

Properties and uses of HX compounds:

Acidity of HX, differences between aqueous / nonaqueous HF, liquid HF as a solvent; anomaly of HF; hydrogen bonding in HF; fluorinated hydrocarbons (CFHs, PTFE)

Interhalogenes: XY, XY3, XY5, XY7: syntheses, structures, and reactivities; bonding in interhalogenes, application of VSEPR theory, hybridization, multicentered bonding

Polyhalide and polyhalonium ions.

oxyacids of the halogenes: HXOn (n=1-4): synthesis, reactivity, acidity, structure and bonding; comparison of HOF and HClO / ClO₄ and BrO₄; uses (bleaching agents, potent oxidizers, chlorates in pyrotechnics, antiseptics, NH ₄ClO₄ in solid boosters, bromatometry)

Oxides of the halogenes: X₂O_n (n=2-7), XO_m (m=1-4): synthesis, structure and properties, oxygen compounds of fluorine

Alkaline earth metals

Historic aspects (discovery, isolation)
occurrence, preparation; physical and chemical properties: comparison with alkali metals, uses; organomagnesium compounds.Oxides, hydroxides, carbonates, sulfates of the alkaline earth metals, hardness of water. Building materials; lime, quick lime, mortar, Sorel cement, marble.

Chalkogenes

Historic aspects (discovery, isolation)
Occurrence, preparation; physical and chemical properties

Oxygen: occurrence in air, water, oxides and salts of oxoacids; Linde process, electrolysis; BaO/BaO₂ process; adsorption. MO scheme of O₂, singlet O₂, atomic O. Ozone: synthesis, reactivity, O3 in the atmosphere / ozone layer.

Compounds of oxygen: water: hydrosphere, physical and chemical properties. H₂O₂: synthe-sis; modern processes; uses: bleach, , oxygen carrier; peroxides, hyperoxides, ozonides.

Sulfur: occurrence of the element (elemental; ores, glances; sulfates; biosphere); production/ mining of sulfur; Frasch process, Claus process, flue gas desulfurization; allotropic forms of sulfur; uses of sulfur: sulfuric acid, sulfur compounds, vulcanization of rubber, matches, etc.

Sulfur compounds: hydrogen compounds: H₂S (occurrence, synthesis, use, removal from natural gas), chemical properties, analytical uses of H₂S. H₂S_n: synthesis, properties, related compounds, complexes. Halogenides: SX_n (n=2,4,6) and S₂X_n (n=2,4,10), thionyl and sulfuryl halogenides. Sulfur oxides: SO_m (m=1-4), S_nO(n=2, 5-10), and S_nO₂ (n=2,7). SO₂: synthesis (ox. of S₈, torrefaction of ores, Müller-Kühne process). properties: redox, acid-base, ligand, liquefaction, liquid SO₂ as a solvent, toxicity of SO₂, smog. Uses: synthesis of SO₃, sulfites sulfite based cellulose digestion, sulfochlorination, bleach, preservative.

SO₃: synthesis (ox. of SO₂ using O₂ and a vanadia based catalyst), properties: acidity, redox. Oxoacids of sulfur: H₂S_nO (n=3,4,5), H₂S₂O_n (n=3-8), polysulfan sulfonic acids H₂S_nO₃, H₂S_nO₆, polysulfuric acids; peroxo derivatives. H₂SO₃: acidity, salts, reducing and oxidizing properties. H₂SO₄: synthesis and uses. Halogenides and oxohalogenides of sulfur: SX, S₂X₂, SX₄, SX_6, SOX₂, SO₂X₂: synthesis, properties, uses. Nitrogen compounds of sulfur: S₄N₄, S₂N₂, (SN)_x, NSX; amidosulfuric acid and derivatives (H₂NSO₃H, (H₂N)₂SO₂, HN(SO₃H)₂, N(SO₃H)₃

Selenium, Tellurium Polonium: occurrence, isolation, historic remarks, uses; allotropic forms; compounds with hydrogen, halogenes, oxygen, chalkogenides, acids

Earth metals

Historic aspects (discovery, isolation).
Occurrence, preparation; physical and chemical properties:

Boron: discovery, isolation, properties, structural features.Borides. Boranes, structure and bonding (closo, nido, arachno, hypho boranes; Wade's rules); B₂H₆. Boron halogenides: syntheses, properties and uses. Oxides of boron, boric acids, borates;boron nitride, amino boranes, borazole.

Aluminum, gallium, indium, thallium:occurrence, discovery, isolation, uses.Fusion electrolysis and preparation of alumina, Bayer process, dry digest of bauxites, acid digests

hydrogen compounds (MH₃, LiAlH₄); halogenides, sub-halogenides (MX); oxides and hydroxides (alumina, corundum, β-alumina, Böhmit, Bayerit, Hydrargillit...), spinels.

Pnicogenes

Historic aspects (discovery, isolation)
Occurrence, preparation; physical and chemical properties

Nitrogen: occurrence, biological importance; physical and chemical properties, production (Linde process), uses.

Phosphorus: occurrence, isolation, uses; allotropic forms (white, red, black); physical and chemical properties.

Nitrogen compounds: hydrogen compounds: ammonia (synthesis and use), hydrazine, hydrazoic acid; nitrides; halogene compounds NX₃, N₂X₄, XN₃; oxohalogen compounds: NOX, NO₂X; oxides (NO, N₂O, NO₂, N₂O₂, N₂O₄, N₂O₅, NO₃).Oxyacids of nitrogen (nitrous, nitric, hyponitrous, peroxynitric acid).

Phosphorus compounds: hydrogen compounds (PH₃, P₂H₄, P_nH_m); phosphides; halogenides (PX₃, PX₅, Berry, P₂X₄); oxo halogenides (POX3), oxides (P₄O_10-n, n=0-4), related acids: phosphinic, phosphonic, phosphoric acids, peroxo acids, oligo-/polymeric phosphates; sulfur compounds of phosphorus; nitrogen compounds of phosphorus (phosphazenes, nitrides); syntheses and uses.

Arsenic, Antimony and Bismuth: hydrides; halides (MX3, MX5, halogeno complexes), oxides, oxo acids, sulfides

Tetreles

Historic aspects (discovery, isolation)
Occurrence, preparation; physical and chemical properties

Carbon: occurrence and production; allotropes of carbon (graphite, diamond, fullerenes...) chemical properties; graphite derivatives, intercalates; fullerene derivatives; other carbon compounds: oxidation states of carbon, hybridizations, carbides; halogen compounds, CFHs, ozone layer, oxo halides; CO, CO₂: technical importance, Boudouard's equilibrium;chalcoge-nides (CS, CS2); nitrogen compounds of carbon ((CN)₂, HCN; synthesis, use, toxicity).

Silicon: occurrence, preparation; physical and chemical properties; compounds of silicon: oxidation states, coordinative geometries; comparison carbon – silicon; hypo- and hypervalent silicon compounds; silicon based ions; silanes (synthesis, use, properties); SiO₂ and its polymorphs; other binary compounds of silicon (SiS₂, Si₃N₄; nitride based high tech ceramics, production and uses); structures and properties of silicates; use of silicates; silicones, Müller-Rochow process; silanoles, silanolates, siloxanes.

Germanium: occurrence, preparation; physical and chemical properties; germanium compounds (GeH₄, GeX₂, GeX₄, GeO, GeO₂ etc.).

Tin: occurrence, preparation; physical and chemical properties; compunds of tin (oxidation states 2 and 4), oligomeric tin cations Snnm+, stannides, Zintl phases, halogenides, stannates uses of tin compounds (biocidal compounds, stabilizers for PVC).

Lead: occurrence, preparation; physical and chemical properties; lead compounds: common states of oxidation (PbH₄, lead mirror method), halides, oxide and sulfide, lead dioxide, lead (II, IV) oxide;acid base properties of lead compounds; pigments, lead white, lead yellow, 'mennige', lead sulfate; lead in dating of minerals.

Glasses:

formation of glasses; major components (sticker, network modifiers, cations in glasses); structural features of glasses; glass technology, uses of glass

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