User:Physchim62/PC Chemistry

Chemical thermodynamics

Definition of the state functions G and F

• Gibbs' free energy G and Helmholz' free energy F
• Thermodynamic identities involving dH, dF and dG
• Gibbs-Helmholz equation

Chemical potential

• Definition of the chemical potential of a pure substance from G
• Expression of dG in terms of temperature, pressure and quantity of matter
• Variation of the chemical potential of a pure substance with pressure and temperature
• Partial molar quantities
• Definition of the chemical potential of a constituant of a mixture (homogeneous or heterogeneous)
• dG = −SdT + Vdp + Σμ_idn_i
• G = Σn_iμ_i
• Gibbs-Duhem equation
• Expression of the chemical potential:
  • for an ideal gas in an ideal mixture
  • for a constituent of an ideal condensed mixture
  • for a solute in a very dilute solution
• Activity, activity coefficient, fugacity, fugacity coefficient

Reaction quantities

• Chemical affinity of a system: definition, direction of spontaneous evolution of a system
• Definition and expression of the thermodynamic equilibrium constant K^o
• Expression of the chemical affinity in terms of the equilibrium constant and the product ‘’Q’’
• Variance, factors which affect an equilibrium (p, T, x_i)
• Variation of the equilibrium constant with temperature: van't Hoff's equation
• Laws of modification of equilibria: effect of temperature, pressure and the introduction of an active or inactive constituent

Phase equilibria of binary mixtures

• Liquid-vapour equilibria: isobaric and isothermal conditions, with total or zero miscibility in the liquid phase
• Solid-liquid equilibria, isobaric conditions, total miscibility in the liquid phase, total or zero miscibility in the solid phase: concept of a defined phase
• Theory of chemical moments

Organic chemistry and spectroscopy

IR and NMR spectroscopy: structure determination

• Principles of IR spectroscopy: qualitative description of normal modes of vibration
• Principles of proton NMR spectroscopy: chemical shift, spin-spin coupling, coupling constant, integration

Organometallics

See Aldehydes and ketones

Alkenes

• Simple Huckel theory: moleculer orbital of ethylene, description of conjugated systems, application to butadiene
• Hydrogenation with heterogeneous catalysis
• Epoxydation with peroxycarboxylic acids
• Hydrolysis of epoxides (acid and base)
• syn-Dihydroxylation with osmium tetroxide
• Preparation of primary alcohols by hydroboration of a terminal alkene
• Ozonolysis
• Diels-Alder reaction: mechanism, frontier orbital interactions

Aromatic hydrocarbons

• Aromaticity
• Geometric and electronic structure of benzene
• Electrophilic aromatic substitution: general mechanism, alkylation, acylation, nitration and halogenation
• Interpretation of the orientation of the substitution of anisole and nitrobenzene
• Holemann's rules

Amines

See Carboxylic acids and their derivatives

Aldehydes and ketones

• Preparation by oxidation of alcohols
• Nucleophilic additions:
  • formation of acetals (with mechanism)
  • reduction by sodium borohydride
  • addition of Grignard reagents
• Tautomerism: keto-enol and aldo-enol equilibria
• α-Reactivity: formation of enolate anions
• Generality of the formation of carbanions α to a π-attracting group
• Reactions of enolate anions:
  • aldol condensation (with mechanism)
  • crotonisation (with mechanisms E1, E2 and E2cb)
• C-alkylation (with mechanism)
• α,β-conjugated carbonyls: conjugated addition, reaction with organolithiums, organ coppers and Grignard reagents
• Wittig reaction

Carboxylic acids and their derivatives

• Preparation of esters:
  • from carboxylic acids and alcohols (with mechanism)
  • by reaction of alcohols with acyl chlorides or acid anhydrides (with mechanism)
• Preparation of amides by reaction of amines with acyl chlorides or acid anhydrides (with mechanism)
• Saponification of esters (with mechanism)
• Hydrolysis of nitriles and amides
• Reduction of esters to primary alcohols by lithium aluminium hydride
• Syntheses with malonic esters

Materials

Structure and organisation of condensed phases

Crystal systems and cohesive forces in crystals

• Solid state: amorphous solids, crystalline solids. Model of the perfect crystal
• Elementary definitions: lattice, site, unit cell, asymmetric unit
• Crystal systems. Z, coordination, density, filling efficiency

Close-packed structures

• Hexagonal close-packed and face-centred cubic structures
• Tetrahedral and octahedral sites in a face-centred cubic structure

Principal types of crystal

Metallic crystals

• Close-packed structures (hcp, fcc) and non close-packed structures (bcc)
• Allotropy
• Macroscopic physical characteristics of the metallic bond

Ionic crystals

• Description of four structures derived from cubic systems: CsCl, NaCl, zinc blende and CaF₂
• Definition of the coordinence of the anion and of the cation
• Radius rules for 1-1 cubic structures

Covalent crystals

• Diamond
• Graphite

Molecular crystals

• Ice (cubic)

Metallic materials

Some principles of the extraction of metals

• Construction and use of Ellingham diagrams: application to pyrometallurgy
• Construction and use of E-pH diagrams: application to hydrometallurgy (lixiviation, purification, cementation)
• Use of current-potential curves: application to the preparation of zinc by electrolysis

Corrosion

• Galvanisation

Organic polymers

Generalities

• Chemical structure of organic macromolecules
• Basic definitions describing these structures: repeating unit, degree of polymerisation, linear chains, branched chains
• Polymolecularity (qualitative discussion)
• Definitions: glass transition, semicrystallinity, glassy state, rubbery state

Polymerisation by steps

• Reactive groups and functionality
• General mechanism

Chain polymerisation

• Active centres
• Radical polymerisation and ionic polymerisation
• Radical polymerisation: general mechanism, rate of polymerisation, order of reaction with respect to the promotor and the monomer
• Anionic polymerisation: Monomers concerned, general mechanism, rate of polymerisation, “living” polymers
• Molecular structure of chain polymers:
  • tacticity
  • isomerism
• Mani differences between polymers produced by the two types of polymerisation: polymolecularity, “living” character, importance of transfer reactions

Diversity of structures

• Condensation copolymerisation
• Chain copolymerisation: statistical copolymer, block copolymer, influence of relative reactivities
• Reticulation reactions

Relationship between structure and properties

• Conformations of an isolated flexible chain in a vacuum, statistical effective radius
• Solubility and expansion
• Mechanical properties:
  • thermoplastics
  • thermosets
  • elastomers