Course Content
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I. Chemical Bonding and Electronic Structure
- Electronic configuration and valence
- Aufbau principle
- Valence shell and core shells
- Noble gas configuration and 8 electron rule
- Covalent vs ionic bonding
- Definition of terms
- Electron count in covalent bonds
- Multiple covalent bonds
- Atomic orbitals and hybridization
- VSEPR principle and bonding geometry
- Tetrahedral geometry and atomic orbitals
- Hybridization of atomic orbitals
- sp3, sp2 and sp hybridization of carbon
- inclusion of lone pairs in VSEPR model
- Sigma and π bonding
- Electronegativity and polarization of covalent bonds
- Resonance
- Formal charge, hypovalency and hypervalency
- Conjugation of π electrons
- Aromaticity
II. Functional groups and Nomenclature
- Hydrocarbons
- Alkanes
- Cycloalkanes
- Alkenes, dienes and polyenes
- Alkynes
- Arenes
- Haloalkanes
- Ethers, Sulfides and Epoxides
- Amines
- Alcohols
- Carbonyls
- Aldehydes
- Ketones
- Carboxylic acids
- Carboxylic acid derivatives
- Esters
- Amides
- Acid Halides
- Anhydrides
- Nitriles
- Imides
- Esters of inorganic acids: phosphates, sulfates, nitrates
- IUPAC rules for nomenclature
- Hydrocarbon rules
- Unsaturation
- Functional group prioritization
- Suffixes and substituent names for functional groups
III. Stereochemistry
- Definition of terms: stereoisomer, chirality, conformation, configuration
- Conformational isomerism
- alkanes
- cyclohexane
- substituted cyclohexane
- Molecular chirality and optical activity
- Configurational isomerism
- Stereogenic carbon and the Cahn-Ingold-Prelog system
- Enantiomers and diastereomers
- E and Z alkenes
- cis- and trans- disubstituted cycloalkanes
- Stereogenicity in atoms other than carbon
IV. Intermolecular interactions and physical properties
- Boiling point and melting point
- Effect of molecular weight
- Polarity and dipole-dipole interactions
- Hydrogen bonding interactions and their effect
- Solubility
- Solvent-solute interactions
- Dipole-dipole
- Hydrogen bonding
- The hydrophobic effect
- Chromatography
- Exploitation of intermolecular interactions
- Common stationary phases: silica and alumina
- forms: TLC, column, HPLC and size exclusion
V. Reactive intermediates: carbocations, carbanions, free radicals
- Carbocations
- Trivalent carbon
- Lack of an octet
- sp2 hydridization
- empty p orbital
- Stability trends
- Resonance stabilization
- By neighboring π electrons
- By neighboring heteroatoms with lone pairs
- Carbanions
- Lone pair on carbon
- Retention of geometry
- Configurational lability
- Stability trends
- Free radicals
- Lack of an octet on C
- Neutrality of free radicals
- Stability trends
VI. Spectroscopy
- Infrared
- Theory
- Symmetry, dipole moments and intensity
- Characteristic stretching frequencies
- Bending and other vibrational motion
- Mass spectrometry
- Theory
- Ionization methods
- Fragmentation reactions
- alpha cleavage
- beta cleavage
- McLafferty rearrangement
- Isotoπc distribution
- NMR
- Theory
- Chemical shift, deshielding and electronegativity
- Diamagnetic anisotropy
- Vicinal coupling
- Idea
- Coupling constant
- Multiplicity (N+1 rule)
- Effects of geometry on coupling constant
- Geminal and 4-bond coupling
- 13C NMR
- Other nuclei (15N, 31P, 19F)
- Integrated spectroscopy problems
VII. Reactivity and the movement of electrons
- Lewis acids and bases; nucleophiles and electrophiles
- Definition of terms: addition, elimination, substitution
- Donation of electrons toward covalent bond
- Use of curved arrow formalism to describe electron movement
- Starts at reactive lone pair (or bond)
- Terminates at midpoint of forming bond
- Alternatively, ends at atom if changing charge state
- Curved arrows in resonance
- Kinetics and Thermodynamics
- Reversibility and irreversibility
- Le Chatelier’s Principle
- Kinetics and transition state energies
- Hammond’s postulate and the use of intermediates
VIII. Acid-Base Reactivity
- Lewis acidity/basicity vs. Brønsted acidity/basicity
- Factors affecting Brønsted acidity
- Electronegativity
- Bond strength to hydrogen
- Inductive effects
- Resonance effects
- Solvent effects
- Quantifying acidity: pKa values
- Representative pKa values of various functional groups
- Solvents and the leveling effect