CHE 495

HYDROCARBON
Ms. Edura Badaruddin
COURSE INFORMATION

COURSE NAME : HYDROCARBON
CHEMISTRY
COURSE CODE : CHE495
PROGRAM : EH220/EH221/EH223
SEMESTER : 2
CREDIT HOURS : 3
CONTACT HOURS : 4
COURSE STATUS : CORE (Passing grade:
C)
PRE-REQUISITE : NIL


SYNOPSIS
This course provides a chemical background of sufficient depth to facilitate an
understanding of the organic chemical processes, which occur in industry. Topics
covered include organic nomenclature, reaction types and mechanisms, biomolecules
and polymers.
OBJECTIVES
Upon completion of this course, the students should be able to:
1. Explain the concept of hybridization in describing bonding between atoms in organic
molecules.
2. Identify and describe the reactions of organic compounds based upon their
functional activity.
3. Analyze chemical reactions and propose plausible chemical reaction mechanisms.
METHODS OF INSTRUCTION
Lecture and Tutorial
Lecture : 3 hours/week
Tutorial : 1 hour/week
ASSESSMENT
Tests and Assignments : 40%
Final Examination : 60%

TEXTBOOK

McMurry, J., 2011. Organic Chemistry. 8
th
ed. Belmont: Brooks Cole

REFERENCES

T.W.G. Solomons, 2008. Organic Chemistry.9
th
ed. Wiley.

Silberberg, M., 2011. Chemistry: The Molecular Nature of Matter and Change. 6
th
ed. New York:
McGraw-Hill.

ADDITIONAL INFORMATION/DETAILS

1. Attendance is compulsory. Students who fail to comply 80% of attendance will be barred from
sitting for the final examination. Absence from lectures, tutorials or tests must be supported with
relevant documentation.
2. Marks will be deducted for late submission of assignment/report at the rate of 50% per week
after the due date.
3. Consultation is by appointment.
4. Any form of cheating and plagiarism in examinations, tests and assignments will be penalized.
Week Duration Topics Activities
1 1
Chapter 1: Structure and Bonding
1.1 Atomic structure
1.2 Valence Bond Theory
1.3 Molecular Orbital Theory
1.4 Hybridization
1.4.1 sp
3

1.4.2 sp
2

1.4.3 sp
Briefing of the course objectives
and lesson plan.
Lecture/ exercise
Read Mc Murry Chapter 1
2 1
Chapter 2: Organic Reaction Types
2.1 Kinds of organic reactions
2.1.1 Addition
2.1.2 Rearrangement
2.1.3 Substitution
2.1.4 Elimination
2.2 Mechanisms
2.3 Describing reactions
Lecture/ exercise
Read Mc Murry p. 184-210,
Chapter 11
3-5 3
Chapter 3: Alkanes, Alkenes and Alkynes
3.1 Structure
3.2 Nomenclature
3.3 Properties
3.4 Synthesis
3.5 Reactions
Lecture/ exercise
Read Mc Murry Chapter
3, 4, 7, 8 & 9
TEST 1 (Chapter 1, 2 and 3)
6-7


1

Chapter 4 : Benzene and Aromaticity
4.1 Structure
4.2 Nomenclature
4.3 Properties
4.4 Synthesis
4.5 Reactions
4.6 Aromaticity
Lecture/ exercise
Read Mc Murry Chapter 15 &16
7

-9

3
Chapter 5 : Organohalides, Alcohols, Phenols,
Carbonyls, Ethers and Epoxides
5.1 Structure
5.2 Nomenclature
5.3 Properties
5.4 Synthesis
5.5 Reactions
Lecture/ exercise
Read Mc Murry Chapter 10,17,
19-20 & p.686-694
9

-10

1
Chapter 6 : Biomolecules (Amino Acid)
6.1 Structure
6.2 Nomenclature
6.3 Properties
6.4 Synthesis
6.5 Reactions
Lecture/ exercise
Read Mc Murry p. 1016-1029,
& 1038-1043
10

-11


Chapter 7 : Monomers and Polymers
7.1 Chain Growth Polymerization
7.2 Step Growth Polymerization
7.3 Polymer Structure and Physical Properties
Lecture/ exercise
Read Mc Murry p. 1207-1208 &
1212-1215
TEST 2 (Chapter 4, 5, 6 and 7)
12-14

3 INTEGRATED PROJECT
CHAPTER 1
STRUCTURE AND BONDING
Chapter 1: Structure & Bonding
1.1 Atomic Structure: The Nucleus
1.2 Atomic Structure: Orbitals
1.3 Atomic Structure: Electron Configuration
1.4 Development of Chemical Bonding Theory
1.5 The Nature of Chemical Bonds: Valence Bond
Theory
1.6 sp
3
Hybrid Orbitals
1.7 sp
2
Hybrid Orbitals
1.8 sp Hybrid Orbitals
1.9 Hybridization of Nitrogen, Oxygen, Phosphorus &
Sulfur
1.10 The Nature of Chemical Bonds: Molecular Orbital
Theory

Summary
1.1 Atomic Structure
Atom:
Proton Positively charged
Neutron Neutral
Electron Negatively charged (negligible mass)
Atom is neutral,
No. of protons = no. of electrons
Diameter of an atom is about 2 10
-10
m (200
picometers (pm)) [the unit angstrom () is 10
-10
m =
100 pm]
The Structure of The Atom
+
N
N
+
-
-
proton
electron
neutron
shell
The Ancient Greeks used to believe that everything
was made up of very small particles. I did some
experiments in 1808 that proved this and called these
particles ATOMS:
Dalton
Atomic number (Z) - number of protons in the
atom's nucleus
Mass number (A) - number of protons plus
neutrons



Isotopes - atoms that have the same atomic
numbers but different numbers of neutrons
different mass numbers


Atomic mass (atomic weight) - weighted
average mass in atomic mass units (amu) of an
elements naturally occurring isotopes
A
Z
X
(protons + neutrons) mass
number
(protons only) atomic
number
1
1
H
2
1
H
3
1
H
deuterium tritium hydrogen
1.2 Atomic Structure: Orbitals
4 kinds of orbitals: s, p, d, and f







Orbitals are organised into different layers
electron shells

Orbitals and Shells
Orbitals are grouped in shells of increasing size and energy.
Different shells contain different numbers and kinds of orbitals.
Each orbital can be occupied by two electrons.
First shell contains one s orbital, denoted 1s, holds only two
electrons.
Second shell contains one s orbital (2s) and three p orbitals (2p),
eight electrons.
Third shell contains an s orbital (3s), three p orbitals (3p), and five d
orbitals (3d), 18 electrons.

p-Orbitals
2 p orbitals within a given shell are oriented in
perpendicular directions: p
x
, p
y
, and p
z

Lobes of a p orbital are separated by region of zero
electron density, a node
1.3 Atomic Structure: Electron
Configurations
Ground-state electron configuration (lowest
energy arrangement) listing of orbitals
occupied by the electrons.

Rules 1:
Lowest-energy orbitals
first: 1s 2s 2p
3s 3p 4s 3d

Aufbau Principle

Rules 2:
Electrons act as they are
spinning around axis,
2 spin orientations: or

Only 2 electrons occupy
an orbital
Pauli Exclusion
Principle
Rules 3:
If 2 or more empty
orbitals of equal energy
are available, 1 electron
occupies with parallel
spins until orbitals are
half-full

Hunds Rule
1.4 Development of Chemical Bonding
Theory
Atoms form bonds because the compound that
results is more stable than the separate atoms.
Ionic bonds in salts form as a result of electron
transfers.
Example: Na
+
Cl
-

Organic compounds have covalent bonds from
sharing electrons (G. N. Lewis, 1916).
Kekul and Couper independently observed
that carbon always has four bonds.


van't Hoff and Le Bel proposed that the four
bonds of carbon have specific spatial
directions.
Atoms surround carbon as corners of a
tetrahedron
Lewis structures (electron dot) show valence electrons
of an atom as dots.
Hydrogen has one dot, representing its 1s electron
Carbon has four dots (2s
2
2p
2
)




Kekule structures (line-bond structures) have a line
drawn between two atoms indicating a 2 electron
covalent bond.


Method of Indicating Covalent Bonds
Note that:
Stable molecule = noble gas configuration
Completed shell, octet (eight dots) for main-group atoms, two
for hydrogen.
Depends on how many additional valence electrons to reach
noble gas configuration.
Carbon has four valence electrons (2s
2
2p
2
), forming four bonds
(CH
4
).
Nitrogen has five valence electrons (2s
2
2p
3
) but forms only three
bonds (NH
3
).
Oxygen has six valence electrons (2s
2
2p
4
) but forms two bonds
(H
2
O).

Non-bonding Electron
Valence electrons not used in bonding are called
non-bonding electrons or lone-pair electrons
Nitrogen atom in ammonia (NH
3
)
Shares six valence electrons in three covalent bonds and
remaining two valence electrons are non-bonding/lone pair
electrons.
Drawing Structures
Drawing every bond in organic molecule can
become tedious.
Several shorthand methods have been developed to
write structures.
1) Condensed structures (Dont have C-H or C-C single
bonds shown. They are understood)
2) Skeletal structures


Skeletal Structure
3 General Rules:

1) Carbon atoms arent usually shown. Instead a
carbon atom is assumed to be at each
intersection of two lines (bonds) and at the end
of each line.

2) Hydrogen atoms bonded to carbon arent
shown.

3) Atoms other than carbon and hydrogen are
shown.
1.5 The Nature of Chemical Bonds:
Valence Bond Theory
2 models to describe covalent bonding:
Valence Bond Theory
Molecular Orbital Theory
Covalent bond forms when two atoms approach each
other closely so that a singly occupied orbital on one
atom overlaps a singly occupied orbital on the other
atom.



H-H bond is cylindrically symmetrical, bond formed by the
head-on overlap of 2 atomic orbitals are called sigma ()
bonds.

Bond Energy
Reaction 2 H H
2
releases 436 kJ/mol
Product has 436 kJ/mol less energy than two
atoms: HH has bond strength of 436 kJ/mol.
(1 kJ = 0.2390 kcal; 1 kcal = 4.184 kJ)
Bond Length
Distance between
nuclei that leads
to maximum
stability.
If too close, they
repel because
both are positively
charged.
If too far apart,
bonding is weak.
1.6 sp
3
Orbitals
Carbon has 4 valence electrons (2s
2
2p
2
).
In CH
4
, all CH bonds are identical (tetrahedral).
sp
3
hybrid orbitals: one s orbital and three p
orbitals combine to form four equivalent,
unsymmetrical, tetrahedral orbitals (sppp = sp
3
),
Pauling (1931)
Structure of Methane

sp
3
orbitals on C overlap with 1s orbitals on 4 H
atoms to form four identical C-H bonds.
Each CH bond has a strength of 439 kJ/mol
and length of 109 pm.
Bond angle bonds specific geometry,
methane: each HCH is 109.5, the
tetrahedral angle.
Structure of Ethane

Two Cs bond to each other by overlap of an sp
3

orbital from each C.
Three sp
3
orbitals on each C overlap with H 1s
orbitals to form six CH bonds.
CH bond in ethane has a strength of 423 kJ/mol
and length of 154 pm.
All bond angles of ethane are tetrahedral value of
109.5.
1.7 sp
2
Orbitals
sp
2
hybrid orbitals: 2s orbital combines with two 2p
orbitals, giving 3 orbitals (spp = sp
2
). This results in a
double bond.
sp
2
orbitals are in a plane with120 angles.
Remaining p orbital is perpendicular to the plane.
Bonds From sp
2
Hybrid Orbitals

Two sp
2
-hybridized orbitals overlap to form a
bond.
p orbitals overlap side-to-side to format a pi ()
bond.
sp
2
sp
2
bond and 2p2p bond result in
sharing four electrons and formation of C-C
double bond.
Electrons in the bond are centered between
nuclei.
Electrons in the bond occupy regions are on
either side of a line between nuclei.
Structure of Ethylene
H atoms form bonds with four sp
2
orbitals.
HCH and HCC bond angles of about 120.
CC double bond in ethylene shorter and stronger than
single bond in ethane.
Ethylene C=C bond length 134 pm (CC 154 pm).
1.8 sp

Orbitals
C-C a triple bond sharing six electrons.
Carbon 2s orbital hybridizes with a single p orbital giving
two sp hybrids.
two p orbitals remain unchanged.
sp orbitals are linear, 180 apart on x-axis.
Two p orbitals are perpendicular on the y-axis and the z-
axis.
Orbitals of Acetylene

Two sp hybrid orbitals from each C form spsp
bond
p
z
orbitals from each C form a p
z
p
z
bond by
sideways overlap and p
y
orbitals overlap similarly
Bonding in Acetylene

Sharing of six electrons forms C C

Two sp orbitals form bonds with hydrogens
Comparison of C-C and C-H
bonds
1.9 Hybridization of Nitrogen and
Oxygen
Elements other than C can have hybridized orbitals
HNH bond angle in ammonia (NH
3
) 107.3
C-N-H bond angle is 110.3
Ns orbitals (sppp) hybridize to form four sp
3
orbitals
One sp
3
orbital is occupied by two nonbonding
electrons, and three sp
3
orbitals have one electron
each, forming bonds to H and CH
3
.
1.10 The nature of chemical
bonds: Molecular Orbital Theory
A molecular orbital (MO): where electrons are most
likely to be found (specific energy and general
shape) in a molecule
Additive combination (bonding) MO is lower in
energy
Subtractive combination (antibonding) MO is higher
energy
Molecular Orbitals in Ethylene
The bonding MO is from combining p orbital
lobes with the same algebraic sign
The antibonding MO is from combining lobes
with opposite signs
Only bonding MO is occupied
Summary
Organic chemistry chemistry of carbon compounds
Atom: positively charged nucleus surrounded by
negatively charged electrons
Electronic structure of an atom described by wave
equation
Electrons occupy orbitals around the nucleus.
Different orbitals have different energy levels and different
shapes
s orbitals are spherical, p orbitals are dumbbell-shaped
Covalent bonds - electron pair is shared between atoms
Valence bond theory - electron sharing occurs by
overlap of two atomic orbitals
Molecular orbital (MO) theory, - bonds result from
combination of atomic orbitals to give molecular orbitals,
which belong to the entire molecule
Sigma () bonds - Circular cross-section and are formed
by head-on interaction
Pi () bonds dumbbell shape from sideways
interaction of p orbitals



Carbon uses hybrid orbitals to form bonds in organic
molecules.
In single bonds with tetrahedral geometry, carbon has four
sp
3
hybrid orbitals
In double bonds with planar geometry, carbon uses three
equivalent sp
2
hybrid orbitals and one unhybridized p
orbital
Carbon uses two equivalent sp hybrid orbitals to form a
triple bond with linear geometry, with two unhybridized p
orbitals
Atoms such as nitrogen and oxygen hybridize to form
strong, oriented bonds
The nitrogen atom in ammonia and the oxygen atom in
water are sp
3
-hybridized
TUTORIAL/ASSIGNMENT
Chapter 1 : Structure and Bonding
Chapter 2 : Alkanes, Alkenes and Alkynes
Chapter 3 : Organic Reaction Types
Chapter 4 : Organohalides
Chapter 5 : Benzene and Aromaticity
Chapter 6 : Alcohols and Carbonyls
Chapter 7 : Biomolecules
Chapter 8 : Polymers
Chapter 1: Tutorial/Assignment
CH
3
S
S
C H
3
NH
2
CH
3
O
O
-
CH
3
O
Dimethyl
disulfide
Acetamide Acetate ion
1) Give the ground state electron configuration for
each of the following elements:
a) Potassium b) Arsenic
c) Aluminium d) Germanium
2) What is the hybridization of each carbon atom
in acetonitrile, C
2
H
3
N?
3) Fill in any nonbonding valence electrons that
are missing from the following structures?
Chapter 1: Tutorial/Assignment
4) Convert the following molecular formulas into
line-bond structures that are consistent with
valence rules:
a) C
2
H
6
O b)C
3
H
7
Br
c) C
2
H
4
O d) C
3
H
9
N
5) What kind of hybridization do you expect for
each carbon atom in the following molecules?
a) Propane b) 2-methylpropane
c) 1- butane-3-yne c) Acetic acid