Chapter - 1 Introduction

1.
1 Organic Chemistry
Definition:
The study of carbon-containing molecules and
their reactions
What happens to a molecule during a

reaction?
A collision
Bonds break/form
WHAT is a bond?
The BIG question: WHY do reactions occur?

We will need at least 2 semesters of your time to
answer this question.
FOCUS
the 1-1
electrons.
Copyright
2012 John Wileyon
&
Klein, Organic Chemistry 1e
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1.1 Organic Chemistry

Why do we distinguish between organic and
inorganic compounds?
Why are organic compounds important?
Copyright 2012 John Wiley &

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1-2
1.2 Structural Theory

In the mid 1800s, it was first suggested that
substances are defined by a specific
arrangement of atoms.
Why is a compounds formula NOT adequate to
define it?
What term do we use to describe different

substances with the same formula?

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1.2 Structural Theory

Atoms that are most commonly bonded to
carbon include N, O, H, and halides (F, Cl, Br,
I).
With some exceptions, each element
generally forms a specific number of bonds
with other atoms:

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1.3 Covalent Bonding

A covalent bond is a PAIR of electrons shared
between two atoms. For example:

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How do potential energy and stability relate?
What forces keep the bond at the optimal

length?
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Atomic Structure
A review from general chemistry:
Protons (+1) and neutrons (neutral) reside in the
nucleus.
Electrons (-1) reside outside the nucleus. WHERE?
Some electrons are close to the nucleus and
others are far away. WHY?
Look at carbon for example. Which electrons are
the valence electrons?
1-7
Why are valence
electrons important?

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Counting Valence Electrons
You can always calculate the number of valence
electron by analyzing the electronic
configuration. Look at phosphorus.
Or, for Group A elements only, just look at the
group number (Roman numeral) on the periodic
table.

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Simple Lewis Structures
For simple Lewis structures:
1. Draw the individual atoms using dots to
represent the valence electrons.
2. Put the atoms together so they share PAIRS of
electrons to make complete octets. WHAT is an
octet?
Take NH3, for example:
Practice with SKILLBUILDER 1.3.

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Simple Lewis Structures
For simple Lewis structures:
1. Draw the individual atoms using dots to
represent the valence electrons.
2. Put the atoms together so they share PAIRS of
electrons to make complete octets. WHAT is an
octet?
Try drawing the structure for C2H2.

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1.4 Formal Charge

What term do we use to describe atoms with
an unbalanced or FORMAL charge?
How does formal charge affect the stability
of an atom?
Atoms in molecules (sharing electrons) can
also have unbalanced charge, which must be
analyzed because it affects stability.
To calculate formal charge for an atom:
Compare the number of valence electrons that
SHOULD be associated with the atom to the
number of valence electrons that are ACTUALLY
1-11an atom.
associated with
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1.4 Formal Charge

Consider the formal charge example below.
Calculate the formal charge on each atom.
or
Carbon SHOULD have 4 valence electrons because it is in

Group IVA on the periodic table.
Carbon ACTUALLY has 8 valence electrons. It needs 8 for its
octet, but only 4 count towards its charge. WHY?
The 4 it ACTUALLY has balance out the 4 it SHOULD have, so
it does not have a formal charge. Its neutral.
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1.4 Formal Charge

Analyze the formal charge of the oxygen atom in the
following:
or
Oxygen SHOULD have 6 valence electrons because it is in

Group VIA on the periodic table.
It ACTUALLY has 8 valence electrons. It needs 8 for its octet,
but only 7 count towards its charge. WHY?
If it ACTUALLY has 7, but it should only have 6, what is its
formal charge?

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1.5 Polar Covalent Bonds

Covalent bonds are electron pairs that exist
in an orbital shared between two atoms.
What do you think that orbital looks like?
Just like an atomic orbital, the electrons
could be anywhere within that orbital region.
What factors determine which atom in the
bond will attract the shared electrons more?
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Covalent bonds are either polar or nonpolar:
Nonpolar covalent bonds: bonded atoms share electrons
evenly
Polar covalent bonds: one of the atoms attracts electrons
more than the other
Electronegativity:
How strongly an atom attracts shared electrons

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Electrons tend to shift away from lower
electronegativity atoms to higher
electronegativity atoms.
The greater the difference in
electronegativity, the more polar the bond.

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Can a bond have both covalent and ionic
character?

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1.6 Atomic Orbitals

General chemistry review:
In the 1920s, quantum mechanics was
established as a theory to explain the wave
properties of electrons.
The solution to wave equations for electrons
provides us with visual pictures called
orbitals.

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1.6 Atomic Orbitals

General chemistry review:
The type of orbital can be identified by its
shape.
An orbital is a region where there is a
calculated 90% probability of finding an
electron. The remaining 10% probability
tapers off as you move away from the
nucleus.

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1.6 Atomic Orbitals

Electrons behave as BOTH particles and waves. How
can they be both?
Maybe the theory is not yet complete.
The theory does match experimental data, and it

has predictive capability.
Like a wave on a lake, an electrons wavefunction can be
(+), (-), or ZERO.

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1.6 Atomic Orbitals

Because they are generated
mathematically from
wavefunctions, orbital regions
can also be (-), (+), or ZERO.
The sign of the wave function has
nothing to do with electrical
charge.
In this p-orbital, there is a nodal

plane. The sign of the
wavefunction will be important
when we look at orbital
overlapping in1-21
bonds.
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1.6 Atomic Orbitals

Electrons are most stable (lowest in energy)
if they are in the 1s orbital?
The 1s orbital is full once there are two
electrons in it.
Why cant it fit more?
The 2s orbital is filled next. The 2s orbital has

a node.
WHERE?

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1.6 Atomic Orbitals

Once the 2s is full, electrons fill into the three
DEGENERATE 2p orbitals.
Where are the nodes in each of the 2p
orbitals?

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1.6 Atomic Orbitals

Common elements and their electron
configurations:
1-24
Practice with SKILLBUILDER
1.6.
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1.6 Atomic Orbitals

What are the rules that govern our placement of
electrons?

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1.7 Valence Bond Theory

A bond occurs when atomic orbitals overlap.
Overlapping orbitals are like overlapping
waves.
Only constructive interference results in a

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bond.
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1.7 Valence Bond Theory

The bond for an H2 molecule results from
constructive interference.
Where do the bonded electrons spend most

of their time?
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1.8 Molecular Orbital Theory

Atomic orbital wave
functions overlap to
form molecular orbitals
(MOs) that extend over
the entire molecule.
MOs are a more
complete analysis of
bonds because they
include both
constructive and
destructive interference.
The number of MOs
created must be1-28equal
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H2 MOs

Why is the antibonding
orbital higher in energy?
When the atomic orbitals
overlap, why do the
electrons go into the
bonding MO rather than
the antibonding
MO?
H2 MOs
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Imagine a He2
molecule. How would
its MOs compare to
those for H2?
How would the energy
of the He2 compare to
2 He?
Why does helium exist
in its atomic form
rather than in
molecular form?
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H2 MOs

Consider the MOs for CHBr3:
There are many areas of atomic orbital overlap.

Notice how the MOs extend over the entire
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molecule.

How many electrons can fit into the areas
represented in (b)?
Depending on the circumstances, we will use

both MO and valence bond theory to explain
phenomena.
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1.9 Hybridized Atomic

Orbitals
Given the electron
configuration for C
and H, imagine how
their atomic
orbitals might
overlap.
Would such orbital
overlap yield
methane?
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Orbitals
To make methane, the C atom must have 4 atomic
orbitals available for overlapping.
If an electron is excited from the 2s to the 2p, will that make
it suitable for making methane?
If four H atoms were to come in and overlap with the

2s and 2p orbitals, what geometry would the
resulting methane have?
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Orbitals
The carbon must undergo hybridization to
form four equal ATOMIC orbitals
The atomic orbitals must be equal in energy

to form four equal-energy symmetrical C-H
bonds.
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Orbitals
Should the shape of an sp3 orbital look more
like an s or more like p orbital?

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Orbitals
To make CH4, the 1s atomic orbitals of the H
atoms will overlap with the four sp3 hybrid
atomic orbitals of C.

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Orbitals
Draw a picture that shows the necessary
atomic orbitals and their overlap to form
ethane (C2H6).
Draw a picture that shows the necessary

atomic orbitals and their overlap to form
water.
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Practice with CONCEPTUAL
CHECKPOINT
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Orbitals
Consider ethene (ethylene).
Each carbon in ethene must bond to THREE

other atoms, so only THREE hybridized
atomic orbitals are needed.

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Orbitals
An sp2 hybridized carbon will have three
equal-energy sp2 orbitals and one
unhybridized p orbital.

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Orbitals
The sp2 atomic orbitals overlap to form
sigma () bonds.
Sigma bonds provide maximum HEAD-ON

1-41
overlap.
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Orbitals
The unhybridized p orbitals in ethene form pi
() bonds, created by SIDE-BY-SIDE orbital
overlap.
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Practice with CONCEPTUAL
CHECKPOINT
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Orbitals
MO theory provides a similar picture:
Remember, red and blue regions are all part of
the same orbital.

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Orbitals
Why is sp2 hybridization not appropriate for
methane (CH4)?

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Orbitals
Consider ethyne (acetylene).
Each carbon in ethyne must bond to TWO
other atoms, so only TWO hybridized atomic
orbitals are needed

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Orbitals
The sp atomic orbitals overlap HEAD-ON to
form sigma () bonds while the unhybridized
p orbitals overlap SIDE-BY-SIDE to form pi ()
bonds.
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Practice with SKILLBUILDER
1.7.
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Orbitals
Which should be stronger, a pi bond or a
sigma bond? WHY?
Which should be stronger, an sp3sp3 sigma

bond overlap or an spsp sigma bond
overlap?

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Orbitals
Explain the different strengths and lengths below.
Practice with CONCEPTUAL CHECKPOINT 1.24.

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1.10 Molecular Geometry

Valence shell electron pair repulsion (VSEPR
theory):
Valence electrons (bonded and lone pairs) repel
each other.
To determine molecular geometry:

1. Determine the steric number.

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To determine molecular geometry:
2. Predict the hybridization of the central atom:
If the steric number is 4, then it is sp3.

If the steric number is 3, then it is sp2.
If the steric number is 2, then it is sp.

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3
sp Geometry
For any sp3 hybridized atom, the four valence
electron pairs will form a TETRAHEDRAL
ELECTRON
GROUPHOW
geometry:
does
Methane has
The bond
four equal bonds, the lone pair of
so the bond
ammonia affect
angles are equal. its geometry?

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angles in oxygen
are even smaller.
WHY?

3
sp Geometry
The MOLECULAR geometry is different from
the ELECTRON GROUP geometry. HOW?
Example
Steric
numb
er
Arrangeme
Hybridizati nt of
on
electron
pairs
Arrangemen
t of atoms
(geometry)
CH4
sp3
Tetrahedral
Tetrahedral
NH3
sp3
Tetrahedral
Trigonal
pyramidal
H 2O
sp3
Tetrahedral
Bent

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2
sp Geometry
Calculate the steric number for BF3.
Electron pairs that are located in sp2
hybridized orbitals will form a trigonal planar
ELECTRON GROUP geometry.
What will be the molecular geometry?

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2
sp Geometry
How many electrons are in borons
unhybridized p orbital?
Does this geometry follow VSEPR theory?

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2
sp Geometry
Analyze the steric number, hybridization,
electron group geometry, and molecular
geometry for this imine?

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sp Geometry
Analyze the steric number, hybridization,
electron group geometry, and the molecular
geometry for the following molecules:
BeH2
CO2

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Summary

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1.11 Molecular Polarity

Electronegativity differences cause induction.
Induction (shifting of electrons WITHIN their
orbitals) results in a dipole moment.
Dipole moment = (the amount of partial charge) x
(the distance the + and - are separated)
Dipole moments are reported in units of debye
(D)
1 debye = 10-18 esu cm
An electrostatic unit of charge (esu) is a unit of charge.
One electron has a charge of 4.80 x 10-10 esu.
Centimeters (cm) are included in the unit because the
distance between the centers of + and charges affects
the dipole.

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Consider the dipole for CH3Cl
Dipole moment () = charge (e) x
distance (d)
Plug in the charge and distance
= (1.056 x 10-10 esu) x (1.772 x

10-8 cm)
Note that the amount of charge
separation is less than what it would
be if it were a full charge separation
(4.80 x 10-10 esu).
= 1.87 x 10-18 esu cm

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Convert to debye

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What would the dipole moment be if CH3Cl
were 100% ionic?
= charge (e) x distance (d)
Plug in the charge and distance
= (4.80 x 10-10 esu) x (1.772 x 10-8 cm)

The full charge of an electron is plugged in
= 8.51 x 10-18 esu cm = 8.51 D
What % of the C-Cl bond is ionic?

Is the C-Cl bond mostly ionic or mostly
covalent?
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Check out the polarity of come other
common bonds:

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Why is the C=O double bond so much more
polar than the CO single bond?

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For molecules with multiple polar bonds, the
dipole moment is the vector sum of all of the
individual bond dipoles.

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It is important to determine a molecules
geometry FIRST before analyzing its polarity.
If you have not drawn a molecule with the proper
geometry, you may not assess the polarity
correctly.
Would the dipole for water be different if it

were linear rather than angular?

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Electrostatic potential maps are often used
to give a visual depiction of polarity.

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Explain why the dipole moment for pentane

equal 0 D.
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1.12 Intermolecular Forces

Many properties such as solubility, boiling
point, density, state of matter, melting point,
etc. are affected by the attractions BETWEEN
molecules.
Neutral molecules (polar and nonpolar) are
attracted to one another through:
Dipoledipole interactions
Hydrogen bonding
Dispersion forces (a.k.a. London forces or fleeting
dipoledipole forces)
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Dipoledipole
Dipoledipole forces result when polar
molecules line up their OPPOSITE charges.
Note that acetones permanent dipole results
from the difference in electronegativity
between C and O.
The dipoledipole attractions BETWEEN
acetone molecules affects acetones boiling
point (BP) and melting point (MP). HOW?

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Dipoledipole
Why do isobutylene and acetone have such
different MPs and BPs?

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Hydrogen Bonding
Hydrogen bonds (H-bonds) are an especially
strong type of dipoledipole attraction.
Hydrogen bonds are strong because the
partial + and charges are relatively large.
Why are the partial charges in the H-bonding
examples below relatively large?

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Hydrogen Bonding
Only when a hydrogen shares electrons with
a highly electronegative atom (O, N, F, or Cl)
will it carry a large partial positive charge.
The large + on the H atom can attract large
charges on other molecules.
Even with the large partial charges, H-bonds

are still about 20 times weaker than covalent
bonds.
Compounds with H atoms that are capable of
forming H-bonds are called PROTIC.
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Hydrogen Bonding
Which of the following solvents are PROTIC
(capable of H-bonding), and which are not?
Acetic acid
Methylene chloride
Diethyl
ether
Dimethyl sulfoxide

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Hydrogen Bonding
Explain why the following isomers have
different boiling points.

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London Dispersion Forces
If two molecules are nonpolar (dipole = 0 D),
will they attract one another?
YES. HOW?
Nonpolar molecules normally have their

electrons (-) spread out evenly around the
nuclei (+), completely balancing the charge.
However, the electrons are in constant
random motion within their MOs.
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The constant random motion of the electrons
in the molecule will sometimes produce an
electron distribution that is NOT evenly
balanced with the positive charge of the
nuclei.
Such uneven distribution produces a
temporary dipole, which can induce a
temporary dipole in a neighboring molecule.

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The result is a fleeting attraction between
the two molecules.
Such fleeting attractions are generally weak.

However, like any weak attraction, if there
are enough of them, they can add up to a lot.
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The greater the surface area of a molecule,
the more temporary dipole attractions are
possible.
Consider the feet of a gecko:
They have many flexible hairs on their feet that
maximize surface contact.
The resulting London dispersion forces are
strong enough to support the weight of the
gecko.

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Explain why molecules with more mass
generally have higher boiling points.

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Explain why more highly branched molecules
generally have lower boiling points.

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1.13 Solubility
We use the principle that like dissolves like.
Polar compounds GENERALLY mix well with
other polar compounds:
If the compounds mixing are all capable of Hbonding and/or strong dipoledipole interactions,
then there is no reason why they shouldnt mix.
Nonpolar compounds GENERALLY mix well

with other nonpolar compounds:
If none of the compounds are capable of forming
strong attractions, then no strong attractions
would have to be broken to allow them to mix.
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1.13 Solubility
We know it is difficult to get a polar
compound (like water) to mix with a nonpolar
compound (like oil):
We cant use just water to wash oil off our dirty
cloths.
To remove nonpolar oils, grease, and dirt, we

need soap.

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1.13 Solubility
Soap molecules organize into micelles in
water, which form a nonpolar interior to
carry away dirt.

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1.13 Solubility
Which attraction is generally stronger?
The attraction between a permanent dipole and
an induced or fleeting dipole,
or
The attraction between a temporary dipole and
an induced dipole (2 fleeting dipoles).
Which attraction is generally stronger?

The attraction between a polar molecule and a
nonpolar molecule,
or
The attraction between two nonpolar molecules?
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1.13 Solubility
Why wont a nonpolar compound readily
dissolve in water?
Is it because the water molecules repel the
nonpolar molecules?

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Chapter - 1 Introduction

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Chapter - 1 Introduction

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1.

What happens to a molecule during a

The BIG question: WHY do reactions occur?

1.1 Organic Chemistry

Why are organic compounds important?

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.2 Structural Theory

What term do we use to describe different

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.2 Structural Theory

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.3 Covalent Bonding

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.3 Covalent Bonding

What forces keep the bond at the optimal

Klein, Organic Chemistry 1e

1.3 Covalent Bonding

Copyright 2012 John Wiley &

1.3 Covalent Bonding

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.3 Covalent Bonding

Take NH3, for example:

Practice with SKILLBUILDER 1.3.

Klein, Organic Chemistry 1e

1.3 Covalent Bonding

Try drawing the structure for C2H2.

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.4 Formal Charge

1.4 Formal Charge

Carbon SHOULD have 4 valence electrons because it is in

Klein, Organic Chemistry 1e

1.4 Formal Charge

Oxygen SHOULD have 6 valence electrons because it is in

Practice with SKILLBUILDER 1.4.

Klein, Organic Chemistry 1e

1.5 Polar Covalent Bonds

Klein, Organic Chemistry 1e

1.5 Polar Covalent Bonds

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.5 Polar Covalent Bonds

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.5 Polar Covalent Bonds

Practice with SKILLBUILDER 1.5.

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.6 Atomic Orbitals

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.6 Atomic Orbitals

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e

1.6 Atomic Orbitals

The theory does match experimental data, and it

Copyright 2012 John Wiley &

Klein, Organic Chemistry 1e