User:Physchim62/PCSI Chemistry

Periodicity

 * Introduction to the quantum numbers: n, l, ml, ms. Existence of quantised energy levels in the atom, degeneracy of these levels.
 * Electronic configuration of an atom or an ion (in the ground state): Pauli’s exclusion principle, Aufbau rules.
 * Construction of the periodic table: structure in blocks.
 * Trends in certain atomic properties: ionisation energy, electron affinity and Mulliken electronegativity.
 * Core electrons, valence electrons.

The quantum model of the atom

 * Probability density for the electron in a hydrogen-like atom.
 * Polyelectronic atoms: orbital approximation, Slater's effective nuclear charge; energies of hydrogen-like and polyelectronic atoms.
 * Atomic radius.
 * Ionic radius.

Electronic structure of molecules

 * Localised covalent bond: Lewis notation.
 * Octet rule.
 * Delocalised covalent bond: mesomerism and resonance.
 * Prediction of the geometry by the VSEPR method.
 * Description of homonuclear diatomic molecules: construction of molecular orbitals by LCAO, orbital overlap; discussion of the MO diagrams of the homonuclear diatomic of the second period.

Low energy interactions

 * Van der Waals forces.
 * Hydrogen bonds.

Rates in chemical kinetics

 * Rates of disappearance of a reactant and of formation of a product, in the case of a closed reactor of uniform composition.
 * Progress of a reaction represented by a single stoichiometric equation.

Kinetic factors. Rate laws

 * Rate law: reaction with integral order; reactions with non-integral order. Examples.
 * Degeneracy of the order.
 * Half-life with respect to a limiting reactant, in the case of zeroth, first and second order reactions.
 * Arrhenius' law (empirical); activation energy.

Reaction mechanisms in homogeneous kinetics

 * Formal kinetics: strictly reversible reactions, parallel reactions, consecutive reactions.
 * Steady-state approximation.
 * Elementary processes, molecular of a process, reaction intermediates, transition state.
 * Qualitative microscopic interpretation of the role of temperature and concentration on the reaction rate.
 * Mechanisms by stages. Rate determining step.
 * Mechanisms in chain. Chain length.

Stereochemistry of organic molecules

 * Newman representations, Cram representations, perspective.
 * Configurational stereoisomerism: Z & E, R & S, enantiomers and diastereomers.
 * Conformation: ethane, butane, cyclopean, and mono- and disubstituted cyclohexanes.

Reactivity of the carbon-carbon double bond

 * Electrophilic addition and radical addition (hydration, hydrohalogenation, halogenation); mechanisms.
 * Cleavage by ozonolysis (without mechanism).

Grignard reagents

 * Preparation of Grignard reagents, experimental conditions.
 * Nucleophilicity and basicity of Grignard reagents.
 * Reactions with carbonyl groups (ketones, aldehydes, esters, acyl chlorides, acid anhydrides), with carbon dioxide, with nitriles and with epoxides.

Carbon-halogen bonds

 * Nucleophilic substitution reactions: SN1 and SN2 limiting mechanisms; stereochemistry.
 * Elimination reactions: E2 limiting mechanism, stereochemistry.

Carbon-nitrogen single bonds

 * Basicity of amines.
 * Nucleophilic reactivity: alkylation (mechanism).

Carbon-oxygen single bonds

 * Acid-base properties of alcohols
 * Preparation of ethers: Williamson reaction (mechanism)
 * Transformation of an alcohol to an monohalogenated derivative: with HX (mechanism); with PX3 and SOCl2 (without mechanism).
 * Intramolecular dehydration of an alcohol under acidic conditions: formation of an alkene.

Models used for the study of transformations

 * Isobaric and isochoric reactors, isothermal and adiabatic reactors.
 * Heat transfer during isochoric and isobaric transformations.

Standard molar quantities

 * Standard states of a pure component: ideal gas and condensed phase; standard molar quantity.
 * Transformation in a closed system: standard internal energy, standard enthalpy, variation with temperature.
 * Sign of the enthalpy change for and endothermic/exothermic reaction.
 * Thermal effects in an isobaric reactor:

Measurement of standard thermodynamic quantities

 * Standard enthalpy change of formation of a pure substance.
 * Discontinuity in &Delta;rH when one of the species changes state.

Equilibria in aqueous solution

 * Concept of an acid/base pair, predominance as a function of pH.
 * Simple pH calculations (common solutions, buffer solutions).
 * Complexes: definition, stability constant (or dissociation constant). Predominance.
 * Sparingly soluble compounds, precipitation criteria, solubility.
 * Redox pairs: electrode potential; Nernst equation.
 * Redox reactions, equilibrium constant, prediction of the direction of a reaction.
 * Titrations: acid-base, redox, compleximetric, precipitation.