MODULE 1

Fundamentals of
Organic Chemistry
Part 1: Atomic Structure
D R . L O R I C O D S . L A P I TA N J R .
DR. CRISTINA E. TIANGCO
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF SANTO TOMAS

MANILA, PHILIPPINES
This powerpoint presentation is developed based
from the following references:
Mc Murry, J.E. Organic Chemistry 9th edition
Mc Murry, J.E. Foundations of Organic Chemistry

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What is Organic Chemistry?
Living things are made of organic chemicals
Proteins that make up hair
DNA, controls genetic make-up
Foods, medicines

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 Origins of Organic Chemistry
Ø Foundations of organic chemistry from mid-1700’s.
Ø Compounds obtained from plants, animals hard to
isolate, and purify.
Ø Compounds also decomposed more easily.
Ø Torben Bergman (1770) first to make distinction
between organic and inorganic chemistry.
Ø It was thought that organic compounds must
contain some “vital force” because they were from
living sources.
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 Origins of Organic Chemistry
ØBecause of “Vital force”, it was thought that
organic compounds could not be synthesized in
laboratory like inorganic compounds.

Ø1816, Chervrut showed that not to be the case, he

could prepare soap from animal fat and an alkali

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 Origins of Organic Chemistry
• 1828, Wohler showed that it was possible to
convert inorganic salt ammonium cyanate into
organic substance “urea”

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Why study Organic Chemistry?
• Organic chemistry is study of carbon compounds.

• Why is it so special?
- 90% of more than 30 million chemical compounds contain
carbon.
- Examination of carbon in periodic chart answers some of
these questions.
- Carbon is group 4A element, it can share 4 valence
electrons and form 4 covalent bonds.

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1.1 Atomic Structure

— Structure of an atom
◦ Positively charged nucleus (very dense, protons and
neutrons) and small (10-15 m)

◦ Negatively charged electrons are in a cloud (10-10 m)

around nucleus

— Diameter is about 2 ´ 10-10 m (200 picometers (pm)) [the

unit angstrom (Å) is 10-10 m = 100 pm]

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1.1 Atomic Structure

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Atomic Number and Atomic Mass

The atomic number (Z) is the number of protons in

the atom's nucleus
The mass number (A) is the number of protons
plus neutrons
All the atoms of a given element have the same
atomic number

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 The Atomic Symbol
A = Atomic mass C = Charge
=# p +#n = + or - values
A C

Z X #

Z = Atomic # # = Number of atoms

in a formula.
#p=#e
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 The Atomic Symbol
A = Atomic mass
6
= # protons + # neutrons
6

- -
X
12
--
+
6 +
+ +
- + +
Z = Atomic number -
= # protons = # electrons
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 The Atomic Symbol
A = Atomic mass C = Charge = +1
= 11
p + 12
n = 23

23 1+

11
Na
Z = Atomic # = p = 11 # = 1 atom in formula.
Sodium
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Why is the atomic weight on the tables
not a whole #?

47 Atomic number
Silver Name of the element

Ag Elemental Symbol

107.87 Atomic mass (weight)

Atomic weight = The average, relative

mass of an atom in an element.
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 Isotopes of Hydrogen
Isotopes = Atoms of the same element but having
different masses.
1 2 3
1H 1 H 1 H
- - -
+ + +

Protium Deuterium Tritium

99.99% 0.01% Trace %
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Isotopes of Hydrogen
1 2 3
1H 1 H 1 H
- - -
+ + +

Average Atomic weight of Hydrogen

= 1.00794 amu
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 Isotopes of Carbon

12 13 14
6 C 6 C C
- 6 -
- - - - -
+ - + +
- + + +
+ + +
+ + +
- + + + + - + +
- - - - - - -
98.89% 1.11% Trace %
Average Atomic weight of C= 12.011 amu
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 Radioactive Isotopes
3 14
H-3 1 H C-14
6
C
- -
- -
+
+ +
+
+
- + +
Nucleus is unstable - -
So falls apart (decays)
Giving radioactive particles
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Radioactive Isotopes
3 14
H-3 1 H C-14
6
C
- -
- -
+
+ +
+
+
- + +
Nucleus is unstable - -
So falls apart (decays)
Giving radioactive particles

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Electronic arrangement
A new layer is
added for each
row or period in
the table.

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Electron arrangement

24
12
Mg
32
18
8 Electrons
2 fill layers
around
nucleus
Low à High

Shells = Energy levels

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 IA IIA

1 4
1 H He
2
7 9
3
Li 4
Be

2, 1 2, 2

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 IA IIA IIIA

1
1 H
11
7 9
Li Be 5
B
3 4

2, 1 2, 2 2, 3

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 IIIA IVA VA

11 12 13
5
B 6
C 7
N

2, 3 2, 4 2, 5

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 IA IIA VIIIA

1 4
1 H He
2

7 9 20

Li 4
Be 10 Ne
3
2, 1 2, 2 2, 8

24 40
23 12Mg 18Ar
11 Na
2, 8, 8
2, 8, 1 2, 8, 2

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 1
1 Valence electrons
1 H Where most chemical
2 Reactions occur.
3
7 9 11
Li 4
Be B
3 5

2, 1 2, 2 2, 3

24 27
12Mg 13Al
23
11 Na
2, 8, 3
2, 8, 1 2, 8, 2

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 1
8
1 Octet Rule 4
1 H He
2 2
9 20
7 Be Ne
3
Li 4
10

2, 1 2, 2 2, 8

24 40
23 12Mg 18Ar
11 Na
2, 8, 8
2, 8, 1 2, 8, 2

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The Octet Rule
ØAtoms are most stable if they have a filled or empty outer
layer of electrons.
ØExcept for H and He, a filled layer contains 8 electrons - an
octet.
ØAtoms gain, lose or share electrons to make a filled or
empty outer layer.
ØAtoms gain, lose or share electrons based on what is
easiest.

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1.2 Atomic Structure: Orbitals
Quantum mechanics: describes electron energies
and locations by a wave equation.
◦ Wave function solution of wave equation
◦ Each wave function is an orbital
◦ A plot of y 2 describes where electron most likely to be

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 Atomic Orbitals
Electron cloud has no specific boundary so we show
most probable area
s (1) p (3) d (5) f (7)

An f orbital

— 4 different kinds of orbitals for e-s

— s and p orbitals most important in organic & biochem
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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

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Orbitals and Shells
1st shell contains one s orbital, denoted 1s, holds 2 e-s
2nd shell contains one s orbital (2s) and three p orbitals (2p), 8
electrons
3rd shell contains an s orbital (3s), three p orbitals (3p), and
five d orbitals (3d), 18 electrons

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p-Orbitals
ØIn each shell there are three perpendicular p orbitals, px, py,
and pz, of equal energy
ØLobes of a p orbital are separated by region of zero electron
density, a node

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1.3 Atomic Structure: Electron
Configurations
Ground-state electron configuration (lowest energy arrangement) of an
atom lists orbitals occupied by its electrons.
1. Aufbau (“build-up”) principle Lowest-energy orbitals fill first:
1s ® 2s ® 2p ® 3s ® 3p ® 4s ® 3d
2. Pauli Exclusion Principle Electrons act as if they were
spinning around an axis. Electron spin can have only two
orientations, up ­ and down ¯. Only two electrons can occupy
an orbital, and they must be of opposite spin to have unique
wave equations
3. Hund's rule If two or more empty orbitals of equal energy
are available, electrons occupy each with spins parallel until all
orbitals have one electron

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 5d
Major trends in electron
filling 4f

5p
Exceptions:
◦ Fill 4s before 3d 4d
◦ Fill 5s before 4 d
5s
◦ Fill 5p before 4f
4p
This is why 3d
transition metals 4s
are assigned as 3p
B group elements.
3s
2p

2s
1s
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Electron Configuration
5d __ __ __ __ __
6s __
4f __ __ __ __ __ __ __
5p __ __ __
4d __ __ __ __ __
5s __
4p __ __ __
4s __ 3d __ __ __ __ __
3px __ y__ z __
3s __
2px __ y__ z __ 7
2s __ Li 1s22s1
3
1s __
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Electron Configuration
5d __ __ __ __ __
6s __
4f __ __ __ __ __ __ __
5p __ __ __
4d __ __ __ __ __
5s __
4p __ __ __
4s __ 3d __ __ __ __ __
3p __ __ __
3s __
2px __ y __z __ 12
2s __
6C 1s22s22p2
1s __
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 Classification by sublevels
s
p
H He

Li Be d B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba Ls Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
f
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Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
L.LAPITAN 2014 38
 Using the periodic table to find
sublevels
s
1 H He
p
2 Li Be 2 B C N O F Ne
3 Na Mg d 3 Al Si P S Cl Ar

4 K Ca 3 Sc Ti V Cr Mn Fe Co Ni Cu Zn 4 Ga Ge As Se Br Kr

5 Rb Sr 4 Y Zr Nb Mo Tc Ru Rh Pd Ag Cd 5 In Sn Sb Te I Xe

6 Cs Ba 5 Ls Hf Ta W Re Os Ir Pt Au Hg 6 Tl Pb Bi Po At Rn

7 Fr Ra 6 Ac

4 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
f 5 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
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Lewis Structures

7 23
1 3
Li Na
11
1 H

H Na Li
Show only Valence Electrons !
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 Lewis Structures

7 23
1 Li 11
Na
1 H 3

H Na Li
Show only Valence Electrons
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 Nonmetals Share e-
1 8
with other nonmetals
H 2 3 4 5 6 7 He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Ga Ge As Se Br Kr
Metals give e- to nonmetals
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 Ionic Bonds
e- moves from Metal à Nonmetal
Stable octets
_
Na + Cl Na+ + Cl
Metal Nonmetal
Cation Anion

+ and - ions attract to form an ionic bond.

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 Covalent Bonds
H + H H H

Cl +
Cl Cl Cl
sharing
O + O O O of
electrons
N + N N N
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Covalent Bonds
H H H-H H2

Cl Cl Cl-Cl Cl2

O O O=O O2

N N N N N2
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Electronegativity
ØElectronegativity refers to the relative tendency of
an atom to draw electrons to itself in a chemical
bond.
ØElectronegativity increases from left to right and
bottom to top across the periodic chart, with F
being the most electronegative element.
ØIn general, when considering electronegativity,
our reference point will be carbon.

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Electronegativity of Common
Elements

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Electronegativity and Bond
Polarity
A covalent bond with electrons shared equally
between the two atoms is called a nonpolar bond.
A covalent bond in which the electrons are shared
unequally is called a polar bond or a polar covalent
bond.

+
H H C Cl Na Cl

Nonpolar Polar covalent Ionic bond

covalent bond bond

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Polar Covalent Bonds
ØIn the carbon—chlorine bond, the electrons are more
strongly attracted to Cl than to C because Cl is more
electronegative than C. This makes the Cl more
‘negative’, and the C more ‘positive. This is depicted
below by the use of a d (delta) symbol. We say that C
has a partial positive (d+) charge, and Cl has a partial
negative (d-) charge.

The bond polarity is symbolized by

an arrow with its head at the negative
end and a cross at the positive end of
the polar bond.
d+ d-
H Cl
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Bonds are on a continuum
from Ionic to Covalent
Carbon almost never forms fully
ionic bonds !

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1.4 Development of Chemical Bonding Theory
ØKekulé and Couper independently observed that carbon
always has four bonds
ØVan't Hoff and Le Bel proposed that the four bonds of carbon
have specific spatial directions
- Atoms surround carbon as corners of a tetrahedron

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 Non-bonding electrons
Valence electrons not used in bonding are called
nonbonding electrons, or lone-pair electrons
◦ Nitrogen atom in ammonia (NH3)
◦ Shares six valence electrons in three covalent bonds
and remaining two valence electrons are nonbonding
lone pair

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Some common geometries
e-’s in 4 directions = 109.5o

H N H H N H N
H
H H
H H
Pyramidal
(109.5o)
Tetrahedral Configuration of Electrons
Trigonal Pyramid Configuration of Atoms
Some common geometries
e-’s in 2 directions = 180o
O=C=O Linear

e-’s in 3 directions = 120o

O
C Trigonal planar
H H
 Formal Charge
Formal charge is the charge calculated for an atom
in a Lewis structure on the basis of an equal sharing
of bonded electron pairs.

Formula for calculating formal charge.

group
number of number of
Formal Charge = number – bonds
–
unshared
in periodic
electrons
table

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Formal Charges
Formal charges in NH4+ and BF4-
..
1 H : F: 7
+ .. – ..
H N H : ..
F B ..F:

H : ..F:
5 3

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 MODULE 1

Fundamentals of
Organic Chemistry
Part 2: Models of Chemical Bonding
D R . L O R I C O D S . L A P I TA N J R .
DR. CRISTINA E. TIANGCO
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF SANTO TOMAS

MANILA, PHILIPPINES
 1.5 The Nature of Chemical Bonds:
Valence Bond 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.

— Two models to describe covalent bonding.

Ø Valence bond theory

Ø Molecular orbital theory

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 1.5 The Nature of Chemical Bonds:
Valence Bond Theory
Valence Bond Theory:
— Electrons are paired in the overlapping orbitals and are attracted to
nuclei of both atoms
◦ H–H bond results from the overlap of two singly occupied
hydrogen 1s orbitals
◦ H-H bond is cylindrically symmetrical, sigma (s) bond

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Bond Energy
Reaction 2 H· ® H2 releases 436 kJ/mol
Product has 436 kJ/mol less energy than two atoms:
H–H has bond strength of 436 kJ/mol.
(1 kJ = 0.2390 kcal; 1 kcal = 4.184 kJ)

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 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

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1.6 sp3 Orbitals and the Structure of
Methane
ØCarbon has 4 valence electrons (2s2 2p2)
ØIn CH4, all C–H bonds are identical (tetrahedral)
Øsp3 hybrid orbitals: s orbital and three p orbitals
combine to form four equivalent, unsymmetrical,
tetrahedral orbitals (sppp = sp3), Pauling (1931)

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1.6 sp3 Orbitals and the Structure of
Methane

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The Structure of Methane
sp3 orbitals on C overlap with 1s orbitals on 4 H atoms to
form four identical C-H bonds
Each C–H bond has a strength of 436 (438) kJ/mol and length
of 109 pm
Bond angle: each H–C–H is 109.5°, the tetrahedral angle.

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 1.7 sp3 Orbitals and the Structure of
Ethane

Two C’s bond to each other by s overlap of an sp3 orbital from

each
Three sp3 orbitals on each C overlap with H 1s orbitals to form
six C–H bonds
C–H bond strength in ethane 423 kJ/mol
C–C bond is 154 pm long and strength is 376 kJ/mol
All bond angles of ethane are tetrahedral

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 1.7 sp3 Orbitals and the Structure of
Ethane

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 1.8 sp2 Orbitals and the Structure
of Ethylene
Øsp2 hybrid orbitals: 2s orbital combines with
two 2p orbitals, giving 3 orbitals (spp = sp2).
This results in a double bond.
Øsp2 orbitals are in a plane with120° angles
ØRemaining p orbital is perpendicular to the
plane

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1.8 sp2 Orbitals and the
Structure of Ethylene

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Bonds From sp2 Hybrid
Orbitals
Ø Two sp2-hybridized orbitals overlap to form a s
bond
Ø p orbitals overlap side-to-side to formation a pi (p)
bond
Ø sp2–sp2 s bond and 2p–2p p bond result in sharing
four electrons and formation of C-C double bond
Ø Electrons in the s bond are centered between
nuclei
Ø Electrons in the p bond occupy regions are on either
side of a line between nuclei

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 Structure of Ethylene
ØH atoms form s bonds with four sp2
orbitals
ØH–C–H and H–C–C bond angles of
about 120°
Ø C–C double bond in ethylene shorter and
stronger than single bond in ethane
Ø Ethylene C=C bond length 134 pm (C–C 154
pm)
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Structure of Ethylene

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 1.9 sp Orbitals and the Structure of
Acetylene
— 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

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1.9 sp Orbitals and the Structure of
Acetylene

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Orbitals of Acetylene
Two sp hybrid orbitals from each C form sp–sp s bond
pz orbitals from each C form a pz–pz p bond by sideways
overlap and py orbitals overlap similarly

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Bonding in Acetylene
Sharing of six electrons forms C ºC
Two sp orbitals form s bonds with hydrogens

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Comparison of C-C and C-H
Bonding

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1.10 Hybridization of Nitrogen and
Oxygen

Elements other than C can have hybridized orbitals

H–N–H bond angle in ammonia (NH3) 107.3°
C-N-H bond angle is 110.3 °
N’s orbitals (sppp) hybridize to form four sp3 orbitals
One sp3 orbital is occupied by two nonbonding electrons, and
three sp3 orbitals have one electron each, forming bonds to H
and CH3.

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1.10 Hybridization of Nitrogen and
Oxygen

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1.11 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

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Molecular Orbitals in Ethylene
The p bonding MO is from combining p orbital lobes with the
same algebraic sign
The p antibonding MO is from combining lobes with opposite
signs
Only bonding MO is occupied

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Molecular Orbitals in Ethylene

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1.12 Drawing Structures
Drawing every bond in organic molecule can become tedious.
Several shorthand methods have been developed to write structures.
Condensed structures don’t have C-H or C-C single bonds shown. They
are understood.
e.g.

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1.12 Drawing Structures
3 General Rules:
1) Carbon atoms aren’t 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 aren’t shown.

3) Atoms other than carbon and hydrogen are

shown
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Learning Check:
Based on the octet rule, which line-bond structures
is/are correct?
H H H H H H H H
H C C C H H C C C H H C C C H H C C C H
H H H H
A B C D
1. A and B
2. A and C
3. B and D
4. Only B
5. Only C
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 Solution:
Based on the octet rule, which line-bond structures
is/are correct?
H H H H H H H H
H C C C H H C C C H H C C C H H C C C H
H H H H
A B C D
1. A and B
2. A and C
3. B and D
4. Only B
5. Only C

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 Learning Check:
Which of these statements concerning p-orbitals is
false?
1. They consist of two equivalent lobes.
2. They are absent from the first shell of atomic
orbitals.
3. They can form π bonds.
4. They only participate in bonding on carbon
atoms.
5. They can hold a maximum of two electrons.
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Solution:
Which of these statements concerning p-orbitals is
false?
1. They consist of two equivalent lobes.
2. They are absent from the first shell of atomic
orbitals.
3. They can form π bonds.
4. They only participate in bonding on carbon
atoms.
5. They can hold a maximum of two electrons.

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Learning Check:
What is the hybridization of the oxygen-bonded
carbon atom in the following molecule?

1. s
2. p H3C
3. sp N C O
4. sp2
5. sp3

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Solution:
What is the hybridization of the oxygen-bonded
carbon atom in the following molecule?

1. s
2. p
H3C
3. sp N C O
4. sp2
5. sp3
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Learning Check:
What type of orbital is not used in constructing the
molecule shown below?
1. s
2. p
O
3. sp
4. sp2 O
5. sp3
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Solution:
What type of orbital is not used in constructing the
molecule shown below?

1. s
2. p O
3. sp
4. sp2 O
5. sp3
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Learning Check:
What is the molecular formula of the molecule
shown below?
1. C8H12O
O
2. C8H11O
3. C8H7O
4. C7H7O
5. C7H10O

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Solution:
What is the molecular formula of the molecule
shown below?

1. C8H12O
O
2. C8H11O
3. C8H7O
4. C7H7O
5. C7H10O
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Learning Check:
Electrons cannot occupy an antibonding molecular
orbital.

1. True
2. False

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 Solution:
Electrons cannot occupy an antibonding molecular
orbital.

1. True
2. False

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Learning Check:
How many hydrogen atoms are present in the naturally-
occurring terpene α-terpinene shown below?

1. 14
2. 15
3. 16
4. 17
5. 18
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 Solution:

How many hydrogen atoms are present in the naturally-

occurring terpene α-terpinene shown below?

1. 14
2. 15
3. 16
4. 17
5. 18

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Learning Check:
Select the best condensed structural formula for
the following molecule:

1. (CH3)2CHCH2COHOHCOH
2. CH3CH3CHCH2C(OH)2CHO HO OH
3. (CH3)2CHCH2C(OH)2CHO
H
4. (CH3)2CHCH2C(OH)2COH
O
5. CH3CHCH3CH2C(OH)2CHO

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 Solution:
Select the best condensed structural formula for
the following molecule:

1. (CH3)2CHCH2COHOHCOH
2. CH3CH3CHCH2C(OH)2CHO
3. (CH3)2CHCH2C(OH)2CHO HO OH
4. (CH3)2CHCH2C(OH)2COH H
5. CH3CHCH3CH2C(OH)2CHO O
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 Learning Check:
What is the correct order of carbon-carbon bond
lengths in ethane, ethylene and acetylene?

1. ethane < ethylene < acetylene

2. ethane < acetylene < ethylene
3. ethylene < ethane < acetylene
4. ethylene < acetylene < ethane
5. acetylene < ethane < ethylene
6. acetylene < ethylene < ethane

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 Solution:
What is the correct order of carbon-carbon bond
lengths in ethane, ethylene and acetylene?

1. ethane < ethylene < acetylene

2. ethane < acetylene < ethylene
3. ethylene < ethane < acetylene
4. ethylene < acetylene < ethane
5. acetylene < ethane < ethylene
6. acetylene < ethylene < ethane

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Learning Check:
What kind of orbital and with how many nodal planes
is shown in the picture below?

1. σ antibonding, two nodal planes

2. σ antibonding, one nodal plane
3. π bonding, one nodal plane
4. π antibonding, two nodal planes
5. π antibonding, one nodal plane

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 Solution:
What kind of orbital and with how many nodal planes
is shown in the picture below?

1. σ antibonding, two nodal planes

2. σ antibonding, one nodal plane
3. π bonding, one nodal plane
4. π antibonding, two nodal planes
5. π antibonding, one nodal plane

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 Learning Check:

What is the best description of bond length?

1. a distance between nuclei that yields the best orbital
overlap
2. a distance between nuclei that yields the smallest
nuclear-nuclear repulsion
3. a distance between nuclei that yields the smallest
electron-electron repulsion
4. a distance between nuclei that yields the largest
electron-nuclei attraction
5. a distance between nuclei that is a compromise of all
electrostatic interactions
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 Solution:
What is the best description of bond length?
1. a distance between nuclei that yields the best orbital
overlap
2. a distance between nuclei that yields the smallest
nuclear-nuclear repulsion
3. a distance between nuclei that yields the smallest
electron-electron repulsion
4. a distance between nuclei that yields the largest
electron-nuclei attraction
5. a distance between nuclei that is a compromise of all
electrostatic interactions

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Learning Check:
What is the O-C-O bond angle in potassium
carbonate, K2CO3?
1. 60°
2. 90°
3. 109.5°
4. 120°
5. 180°
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 Solution:
What is the O-C-O bond angle in potassium
carbonate, K2CO3?
1. 60°
2. 90°
3. 109.5°
4. 120°
5. 180°

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 MODULE 1

Fundamentals of
Organic Chemistry
Part 3: Acid - Base Chemistry
D R . L O R I C O D S . L A P I TA N J R .
DR. CRISTINA E. TIANGCO
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF SANTO TOMAS

MANILA, PHILIPPINES
 Acidity and Basicity
There are three definitions of Acids and Bases: the Arrhenius
definition, the Bronsted-Lowry definition, and the Lewis
definition.

Arrhenius: An acid is a substance that dissociates in water to

give H3O+, and a base is a substance that dissociates in water
to give OH-.
Bronsted-Lowry: An acid is a species that can donate a proton,
and a base is a species that can accept a proton.
Lewis: An acid is an electron pair acceptor, and a base is an
electron pair donor.

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Acidity and Basicity
H2SO4 + H2O HSO4 + H3O

HCl + NaOH NaCl + H2O

BF3 + NH3 H3N BF3

Do not forget that when an acid reacts it forms a
conjugate base, and when a base reacts if forms a
conjugate acid!

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 Acidity and Basicity
The strength of both Bronsted-Lowry and Arrhenius acids is
expressed by the extent of their ionization in water. The general
reaction of an acid (HA) with water is as follows:

Ka
HA + H2O H3O + A
where Ka represents the acid-dissociation constant.
+ -
[H3O ][A ]
Ka =
[HA]
The magnitude of Ka represents the relative strength of the acid. The
stronger the acid, the more it dissociates, giving a larger Ka.

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Acidity and Basicity
Strong Acids: Are almost completely ionized in water; Have Ka’s
greater than 1.
Weak Acids: (most organic compounds); have Ka’s less than 10-4.
Ka’s are often expressed on a logarithmic scale: pKa = -log10Ka
For water:

H2O + H2O OH + H3O

and
+ --14
[H3O ][OH ] 1.00 x 10 -16
Ka = = = 1.8 x 10
[H2O] 55.6 mol/L
The logarithm of 1.8 x 10-16 is -15.7, and the pKa of water is 15.7
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Acidity and Basicity
Key Points!
1. Strong acids generally have pKa values of ~ 0.
2. Weak acids generally have pka values of > 4.
3. The weaker the acid, the larger the pKa.
4. The weaker the acid, the smaller the Ka.

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Acidity and Basicity
Predicting the direction of Acid/Base Equilibria:
In order to predict the direction of acid/base equilibria, it is important to
remember the following:
1. Acid base reactions favor formation of the weaker acid and the weaker base.
2. The stronger the acid, the weaker its conjugate base.
3. The weaker the acid, the stronger its conjugate base.

• Weak is favored!
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Acidity and Basicity
Predicting Acidity
In general, the more stable a conjugate base is, the
more acidic the acid from which it came.

There are three factors that affect the stability of

conjugate bases. These are electronegativity, size, and
resonance.
Electronegativity: The more electronegative an element
is, the more easily it bears a negative charge, giving a
more stable conjugate base, and a stronger acid.

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 Acidity and Basicity
Electronegativity C < N < O < F
electronegativity increases
Stability - - - -
CH3 < NH2 < OH < F

Acidity H-CH3 < H-NH2 < H-OH < H-F

acidity increases

- - - -
Basicity CH3 > NH2 > OH > F
basicity increases

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Acidity and Basicity
Size: The negative charge of an anion is more stable if is spread
over a large region of space. Within a column of the periodic table,
acidity increases down the column, as the size of the elements
increases.
H-F < H-Cl < H-Br < H-I
Acidity acidity increases

- - - -
Stability F < Cl < Br < I

size increases

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Acidity and Basicity
Resonance Stabilization: A conjugate base of an acid is
more likely to form if it can be stabilized by resonance.
CH3CH2 O
ethoxide ion from ethanol
(pKa = 16)

O O

H3C C O H3C C O

acetate ion from acetic acid (pKa = 4.74)

O O O

H3C S O H3C S O H3C S O

O O O

methanesulfonate ion from methanesulfonic acid (pKa = -1.2)

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