User:Physchim62/PC Chemistry

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 = &minus;SdT + Vdp + &Sigma;&mu;idni
 * G = &Sigma;ni&mu;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 Ko
 * Expression of the chemical affinity in terms of the equilibrium constant and the product ‘’Q’’
 * Variance, factors which affect an equilibrium (p, T, xi)
 * 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

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
 * &alpha;-Reactivity: formation of enolate anions
 * Generality of the formation of carbanions &alpha; to a &pi;-attracting group
 * Reactions of enolate anions:
 * aldol condensation (with mechanism)
 * crotonisation (with mechanisms E1, E2 and E2cb)
 * C-alkylation (with mechanism)
 * &alpha;,&beta;-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

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

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)

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

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