UNIT 4

shape of the molecules

- geometric shape of molecules
- each molecule has a particular shape
- 3-dimensional, not flat
LEWIS STRUCTURE
- representation of the structure of
electrons using dots
- dots = valence electrons
Duet rule - shares 2 electrons only
*hydrogen and helium do not need to
comply to octet rule
Octet rule - shares 8 electrons (C, N, O, F)
*exempted to octet rule - B, Be, Li (less
than 8 electron in total); P, S (too much electron,
d-block)
Electron pairs
- lone pairs - localized/isolated
- bonding pairs - between atoms
Drawing a Lewis structure
1. determine number of valence electrons
- cation - subtract one electron
- anion - add one electron
*polyatomic ions - covalent bond
2. determine the connectivity of atoms
3. connect by single bonds
*central atom - least electronegative
4. show electrons as single line;
nonbonding electrons as dots
5. single bond - one pair of electrons; 1
sigma
double - 2 pairs; sigma & pi
triple - 3 pairs; 2 pi & 1 sigma
FC = valence e- - nonbonding e- - no. of bonds
*neutral/no FC/0 FC = preferable
*large FC = less plausible
*negative FC should be placed on more
electronegative atoms (for polyatomic ions)
EXCEPTIONS TO OCTET RULE
- PERIOD 2 elements using 2s and 2p
orbitals FOLLOW octet rule (CNOF)
- period 3 elements have: (do not follow)
1 3s orbital
3 3p orbitals
5 3d orbitals (PSCl)
- these nine orbitals can accommodate
more than eight electrons, by using 3d
orbitals
*d-blocks = transition metals
HYBRIDIZATION
- Mixing of two or more atomic orbitals to
form special (hybrid) orbitals for bonding
- hybrid orbitals are used to form sigma
bonds
- unhybridized = pi bonds
s orbital - sphere shape
p orbital - dumbbell shape
d orbital - four-leaf clover

FORMAL CHARGE
- method to determine whether lewis
structure is correct
- one compound may form 2 lewis
structures
- sum of FC must equal the charge on the
molecule/ion

*sigma is stronger than pi

*Mixing the s and p orbitals yields two
degenerate orbitals that are hybrids of the two
# of # of
orbitals. arrangement molecular
class atoms lone
sp hybrid orbital of e- pairs geometry
bonded pairs

linear linear
180 180

sp2 hybrid orbital AB2 2 0

trigonal
planar
trigonal planar 120
120
sp3 hybrid orbital
AB3 3 0

trigonal planar bent

120
VSEPR
- Valence Shell Electron Pair Repulsion AB2E 2 1
Model
- structure around a given atom is
determined principally by minimizing
electron pair repulsions
tetrahedral
- predicts geometries of molecules tetrahedral
*lone pair repel more than bonding pair 109.5
*electrons move in order to minimize repulsion
AB4 4 0

trigonal
tetrahedral
pyramidal
109.5

AB3E 3 1

tetrahedral
AB2E2 2 2 bent
109.5
regions of distribution bond
shape *There are no stable AXE4, AX3E3, AX2E4 or
e- density of e- density angle
AXE5 molecules.
2 linear 180 linear *All bonds are represented in this table as a line
whether the bond is single, double, or triple.
linear
trigonal *Any atom bonded to the center atom counts as
3 120 bent
planar one domain, even if it is bonded by a double or
trigonal planar
triple bond. Count atoms and lone pairs to
linear determine the number of domains, do not count
bent bonds.
4 tetrahedral 109.5
trigonal pyramid *number of bonded atoms + lone pairs = total
tetrahedral
number of domains
linear
90
trigonal t-shape
5 and
bipyramid see-saw
120
trigonal bipyramid

square planar
6 octahedral 90 square pyramid
octahedral
 UNIT 5
organic compound
- compounds of carbon and hydrogen and
its derivatives
- c covalently linked to mostly H, N, O
(sometimes: S, P, halogens[FClBrI])
- 85% of all known compounds are organic
organic chemistry
- study of compounds of carbon
carbon
- backbone of organic compounds
- abundant in the world
- we are made up of carbon
- has 4 valence electrons and form 4
covalent bonds
- able to bond with one another to form
long chains and rings
- only element that has the ability to form
immense diversity of compounds
CLASSES OF ORGANIC
COMPOUNDS/FUNCTIONAL GROUPS
functional groups
- give identity to organic compound
- sites of predictable chemical reactions
- determine the chemical and physical
properties of a molecule
- serve as units to classify organic
compounds into families
- basis in naming organic compounds
7 common functional groups (aakceaa)
- alcohol
- aldehyde
- ketone (has double bond oxygen)
- carboxylic acid
- ester
- amide
- amine (triple bond C to N)

organic inorganic

covalent
low melting point
insoluble to water
soluble in organic solvents
do not conduct electricity
almost all burn and
decompose
slow reactions
ionic
high melting point
soluble in water
insoluble in organic
solvents
conduct electricity
very few burn
fast reactions

STRUCTURE OF ORGANIC COMPOUNDS

molecular formula - number of atoms of each
element; sum of atoms
structural formula - show atoms and bonds
expanded struc - separate h
condensed struc - combined h
skeletal - no atoms, just bonds

STRUCTURAL EFFECTS
- Resonance
- Hyperconjugation
- Inductive effect
- Steric effect
purpose: stability & reactivity
Resonance
types electron delocalization:
- π Delocalization
- lone pair delocalization
- σ Delocalization (Hyperconjugation)
*Electron pair(s) are shared between more than
two atoms (electrons are delocalized).
*Structural forms = contributing/resonance/
canonical structures
*Resonance hybrid = “Actual” structure; hybrid
of all resonance structures
conditions for electron delocalization:
- conjugated system (alternating double
bonds); double bonds with single bond in
between
- pi bond next to positive charge
- lone pair next to positive charge
- pi bond next to lone pair
Drawing resonance structures
1. The curved arrows show the movement
of electron pairs not of atoms nor
charges.
2. Multiple curved arrows point will flow in
the same direction.
3. Electrons should flow toward positive
charges and away from negative
charges. (TPAN)
 4. observe octet rule Inductive Effect
5. less electronegative to more - displacement of electrons forming a
electronegative (exceptions if the less covalent bond towards the more
electronegative has a positive charge) electronegative atom/group
- cause hydrogen to be reactive
Hyperconjugation - decreases with distance
- sigma bond delocalization
- “no bond resonance”
- occurs when the σ bond (C-C or C-H) is
adjacent to carbon with a π bond or an
empty p orbital
- shifting of sigma electrons to vacant p
orbital to increase stability

*Electrons delocalized due to partial overlapping

of sigma bond orbital and pi-bond orbital or
empty p-orbitals. types of inductive effect
*Electron delocalization results to an increased electron withdrawing/attracting
stability of the molecule. - x more e.neg
*more C-H bonded in double-bonded carbon - electrons attracted to x
atom = higher hyperconjugation = more stability
*Overlap of σ orbital of C – H bond with π orbital
of adjacent C – C double bond
*C – H possesses partial ionic character and its substituents:
electrons get delocalized into the adjacent π - with excess positive charges
system. - those with electronegative atoms
*Stability of alkenes will increase with increase - groups exhibiting orbital
opportunity for hyperconjugation. electronegativity
*any carbon attached to a double bond is sp2 - those with easily polarizable
valence electrons
electron releasing/donating
- c more e.neg
- electrons attracted to c

substituents:
- alkyl groups
- negative groups

*all carbons included in the double bond lang

 Factors Affecting Effect
Acidity/Basicity

Charge if positive:
↑Acidity
↓basicity

Steric Effect Electronegativity across the period:

- spatial environment around a functional ↑acidity
group, where many atoms/groups ↑electronegativity
situated near the functional group
Polarizability down the group:
hindering the accessibility of other ↑acidity
molecules to the functional group ↑polarizability
steric repulsion
- crowding of groups into one another Resonance Effect ↑acidity = more stable conjugate
- effect of bulkiness base
↑electron density on the N of
amine = ↑basicity
Resonance stabilization
decreases basicity

Inductive Effect ↑acidity = electron withdrawing

subs. stabilizes negative charge
*lone pairs like to have more space of conjugate base
↑acidity if:
ACIDITY AND BASICITY - larger no. of e.neg
substituents
Bronsted-Lowry
- more e.neg the
- acid = proton donor substituent
- base = proton acceptor - closer the
Lewis electron-withdrawing
- acid = electron pair acceptor group to COOH
- base = electron pair donor Electron-releasing substituent:
↑basicity
pKa
↑electron density on the N of
- measure of acid strength
amine
- low pKa = high acidity = low basicity Electron-withdrawing subs:
↓basicity
*Structural effects, which stabilizes the ↓electron density on the N of
conjugate base, will increase acidity. amine
*When an acid becomes a conjugate base, the
Hybridization ↑s-character = closer electrons
stability of the new lone pair on the conjugate effect to nucleus = ↓energy = ↑stable
base is a factor in determining how favorable ↑s-character = ↑acidity
the reaction will be.
 - increases the stability of the conjugate
base because the negative charge can
be delocalized

Inductive Effect
- Electron-withdrawing substituent
stabilizes the negative charge of the
conjugate base, increasing acidity
- Electron-releasing substituent
Polarizability destabilizes the negative charge of the
- ease of distorting the electron conjugate base, decreasing acidity
distribution in the atom/molecule
- more spread out charge = more stable
negative charge
- high charge density = less stable

Resonance Effect
 exercises

Hybridization Effect
- Increasing the “s-character” of the
orbital, the closer the electrons will be to
the nucleus, and the lower in energy (=
stable) they will be
 UNITS 6-7 Constitutional Isomers
- same molecular formula but different
Hydrocarbon structures
- compound composed of carbon and example:
hydrogen

Cyclic hydrocarbon
- a hydrocarbon that contains carbon
atoms joined to form a ring

Cycloalkane
- - a cyclic hydrocarbon in which all carbons
of the ring are saturated
Alkanes Alkenes Alkynes - have only single bonds
- more stable = greater angle
single bond double bond triple bond -
*Cycloalkanes with ring sizes of from 3 to over
saturated unsaturated unsaturated
30 carbon atoms are found in nature
hydrocarbons hydrocarbons hydrocarbons
*Five-membered (cyclopentane) and
sp3 sp2 sp six-membered (cyclohexane) rings are
especially abundant in nature.
tetrahedral trigonal linear (180)
(109.5) planar (120) cyclopentane
- 2nd most stable
methane, ethylene acetylene
- boat conformation
ethane
cyclohexane
- most stable
Newman projection - chair conformation
- avoid repulsion & steric effect - six C-H bonds are equatorial
- less steric effect = more stable - six C-H bonds are axial

axial bond - parallel to axis

equatorial bond - perpendicular to axis
*equatorial is more stable than axial
Cis/Trans Isomers for Cycloalkane - blue flame = complete combustion
cis - same side - soot is composed of carbon
trans - opposite side *Oxidation of hydrocarbons, including alkanes
and cycloalkanes, is the basis for their use as
energy sources for heat

Halogenation/Free Radical
*Halogenation of an alkane is a free radical
substitution reaction.
*solid wedge = towards self *merong heterolytic cleavage
*jagged wedge = away from self
heterolytic cleavage - one atom gets both of the
shared electrons
Stereoisomers homolytic cleavage - electrons in the bond are
- isomers that differ in spatial arrangement divided equally between the products
of atoms, rather than order of atomic
connectivity Halogenation
- Cis-trans isomers are one type of - introduce halogen to alkanes
stereoisomer
Steps:
*trans are more stable because there is less 1. Initiation
steric effect 2. Propagation
3. Termination
cis-trans in alkenes
*Because of restricted rotation about a
carbon-carbon double bond, an alkene with two
different groups on each carbon of the double
bond shows cis-trans isomerism.

*if flipped but still looks the same, it is not

cis-trans isomerism
*alkanes undergo rotation
*alkenes change position

REACTIVITY OF ALKANES & CYCLOALKANES

Combustion
- product: CO2 + H2O
Reactions of Alkenes
*Most alkene addition reactions are exothermic.
*products = more stable (lower energy)
*rate of reaction depends on activation energy
- ↑carbon = ↑oxygen *many alkene addition reactions require a
- yellow flame = incomplete combustion = catalyst
formation of soot
 less dense than
water

Boiling lower boiling point physical properties

Point than those of are similar to those
almost any other of alkanes with the
type of compound same carbon
Markovnikov’s rule of the same skeletons
- when an unsymmetrical reagent adds to molecular weight
an unsymmetrical alkene, the more
positive part of the agent goes to the *alkanes & alkenes’ boiling point depend on
carbon that has more hydrogen atoms number of carbon & structure
- H adds to the less substituted carbon
and OH adds to the more substituted branched alkanes = lower boiling point
carbon straight alkanes = higher boiling point bcs of
Van der Waals forces

Physical Properties
Alkane Alkene & Alkyne

Solubility insoluble in water

liquid alkanes are soluble w each other

soluble to other nonpolar orgcomps

Polarity nonpolar

London dispersion forces

Density ave density: room temp density:

0.7g/mL less than 1.0g/mL

higher-molecular-wei
ght alkanes is about
0.8 g/mL