CHAPTER 1: A REVIEW OF GENERAL CHEMISTRY
 Organic chemistry is study of carbon-containing
molecules and their reactions
o Carbon commonly bonded to N, O, H and
halides F, Cl, Br, I
o Each element generally forms specific
number of bonds: mono, di, tri, tetravalent
 During a reaction, molecules collide, transfer of
electrons breaks bonds and forms new bonds
 Structural theory: substances defined by specific
arrangement of atoms, not simply formula
 Constitutional isomers: same formula but different
structures
BONDING
 Valence electrons: electrons in outermost shell are
involved in bonding
 Electronegativity: how strongly atom attracts
shared electrons
o Increasing EN left to right, down to up,
with F as most electronegative atom
 Covalent bonding: atoms share pair of electrons
(EN difference < 0.5)
o Potential energy 0 at high internuclear
distance, then most negative at optimal
length, then increase exponentially as
internuclear distance decreases
o Forces keeping bond at optimal length:
attractive btw nuclei and electrons,
repulsive btw nuclei and btw electrons
 Polar covalent bond: atoms share pair of electrons
(EN difference 0.5-1.7)
o Partial negative, partial positive
o Greater EN difference, the more polar
 Ionic bond: electrons not really shared; more EN
atom owns electrons (EN difference >1.7)
o Some bonds, e.g. EN difference 1.5, on
border btw polar covalent and ionic, so can
be written either way
 Simple Lewis structures:
o Draw individual atoms with dots to
represent valence electrons
o Connect so share pairs of electrons to
make complete octets
 Formal charge: number of valence electrons
needed to be neutral – number of electrons that
molecule owns (based on bonding pattern)
o In bond, molecule only owns one electron
ATOMIC ORBITALS
 Quantum mechanics established as theory to
explain wave properties of electrons
o Electrons behave as both particles and
waves; maybe theory not yet complete
o However, theory matches experimental
data and has predictive capability
 Solutions to wave equations are wave functions
o 3D plot of (wave function)2 gives image of
atomic orbital
o Like ocean wave, wave function can have +
or – value or zero (node) around average
 Atomic orbital: “cloud of electron density”
o Type of orbital defined by shape (s,p,d etc.)
o Orbital shape is 90-95% of space where
electron “probably” is
 Electron density: probability of
finding an electron
o Every orbital can only have 2 electrons
o Orbitals of equal energy are degenerate
o Since orbitals generated from
wavefunctions, orbital regions can be -, +,
or zero, but has nothing to do with
electrical charge (e.g. nodal plane of p)
 Rules for filling orbitals:
o Aufbau principle: fill from lowest energy to
highest energy
o Pauli exclusion principle: no 2 electrons
can have same 4 quantum numbers (i.e.
must be opposite spin)
o Hund’s rule: degenerate orbitals are filled
with one electron before doubly occupied,
and all singly occupied have same spin
THEORIES OF ORBITAL BONDING
 Valence bond theory: bond occurs when atomic
orbitals overlap
o If electron ‘waves’ constructively interfere,
then bond will form
o If electron ‘waves’ destructively interfere,
then node (no bond) will form
 Electrons spend most time in overlapping atomic
orbital space
 Molecular orbital theory: atomic orbital
wavefunctions overlap to form molecular orbitals
(MOs) that extend over entire molecule
o More complete analysis of bonds because
include both constructive and destructive
interference
o Number of MOs created must be equal to
number of AOs that were used
 Antibonding MO has vertical node but bonding MO
does not, thus antibonding has higher energy
 o In ground state, electrons go to bonding
MO to achieve lower energy state while
the higher energy ones remain empty
 The highest occupied MO (HOMO) and lowest
unoccupied MO (LUMO) are in play when
undergoing chemical reaction
HYBRIDIZATION
 In excited state, to make equivalent bonds,
undergo hybridization to form degenerate AOs
 Hybridized orbitals:
o Shape of sxpy orbital results from having
(x/(x+y))% s-character and (y/(x+y=))% p-
character
o Overlap with other orbitals to form sigma
bonds; the more s-character, the shorter
bond will be (sp3 longest)
 Pi bonds are formed by side-by-side overlap
o Weaker than sigma bonds because sigma
requires almost twice amount of bond
energy to break it
o Look at structure of sigma versus pi
bonding versus antibonding MO
GEOMETRY
 Valence shell electron pair repulsion (VSEPR
theory): lone and shared pairs repel
 Steric number: number of bonds + lone pairs
o Translates to hybridization of central atom
3 2
(e.g. 4 is sp , 3 is sp )
 Electron geometry includes lone pairs
o Octahedral, trigonal bypyramidal,
tetrahedral, trigonal planar, linear
 Molecular geometry only includes atoms
o Square pyramidal, square planar, T-shape,
seesaw, bent
o # of geometries = steric number - 1
DIPOLES
 Induction: shifting of electrons within orbital
 Induction results in dipole moment, which is equal
to (amount of partial charge) x (the distance + and
- are separated)
o In units of debye, 1 D = 10 esu*cm-18
 Ionic character: actual/if 100% ionic * 100%
o The charge separation of actual is less than
full charge separation (charge of electron,
4.80*10-10esu)
o Higher ionic character, more polar
 Net dipole moment of molecule vector sum of
individual bond dipoles
o Dependent on molecular geometry
 Electrostatic potential maps: visual depiction of
polarity based on colour
INTERMOLECULAR FORCES
 Physical properties (solubility, density, state of
matter, BP, MP) affected by molecular attractions
 Neutral molecules (polar and nonpolar):
 London dispersion forces: induced, transient dipole
moment
o Electrons spread evenly around nuclei, but
in constant random motion with MOs
o Random motion will sometimes produce
electron distribution not evenly balanced
around nuclei
o Temporary dipole can induce temporary
dipole in neighboring molecule
o Greater SA means more temporary dipole
attractions possible (e.g. feet on Gecko’s
feet, molecules with higher mass,
molecules with less branching because
branching means less SA)
 Dipole-dipole interactions: when polar molecules
line up opposite charges. More polar means
stronger interactions
 Hydrogen bonding: btw H bonded to high EN atom
(O, N, F) and lone pair on another high EN atom.
Strong type of dipole-dipole because partial + and
– charges are relatively charge (only for high EN
atoms). Still ~20 times weaker than covalent bonds
o Found btw DNA strands and for alpha helix
o Solvents that engage in H-bonding are
protic; do not are aprotic
SOLUBILITY
 Polar molecules generally mix well with other polar
compounds, same for nonpolar compounds
o If no compounds capable of forming strong
attractions, no strong attractions would
have to be broken to allow them to mix
 Soap has polar (hydrophilic) and nonpolar
(hydrophobic group)
o Organize into micelles in water, forming
nonpolar interior to carry away dirt and
other nonpolar molecules