CH 01

Organic Chemistry
Second Edition
David Klein
Chapter 1
A Review of General Chemistry: Electrons, Bonds,
and Molecular Properties
Copyright 2015 John Wiley & Sons, Inc. All rights reserved.
Klein, Organic Chemistry 2e
1.1 Organic Chemistry

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 ON THE ELECTRONS
Copyright 2015 John Wiley & Sons, Inc. All rights reserved. 1-2
1.1 Organic Chemistry

Why do we distinguish between organic
and inorganic compounds?
Why are organic compounds important?
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?
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
Practice with SkillBuilder 1.1
1.3 Covalent Bonding

A covalent bond is a PAIR of electrons
shared between two atoms. For example
1.3 Covalent Bonding

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

length?
1.3 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?
Why are valence electrons important?
1.3 Counting Valence

Electrons
You can always calculate the number of
valence electron by analyzing the econfiguration. Look at phosphorus.
Or, for Group A elements only, just look at
the Group number (Roman Numeral) on the
periodic table
1.3 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

Copyright 2015 John Wiley & Sons, Inc. All rights reserved.1-10
1.3 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
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 associated with an atom
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 has1-13
balance out
the
4 Chemistry
it
Klein,
Organic
2e
1.4 Formal Charge
Analyze the formal charge of the oxygen

atom.
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
1-14 it shouldKlein,
only
have
6,2e
Organic
Chemistry
1.5 Polar Covalent Bonds
Covalent bonds are electrons 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?
Covalent bonds are either polar or nonpolar

Nonpolar Covalent bonded atoms share electrons
evenly
Polar Covalent One of the atoms attracts
electrons more than the other
Electronegativity - how strongly an atom

attracts shared electrons
Electrons tend to shift away from lower

electronegativity atoms to higher
electronegativity atoms.
The greater the difference in

electronegativity, the more polar the bond.

Can a bond have both covalent and ionic
character?
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
1.6 Atomic Orbitals
General Chemistry review

The type or orbital 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
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.
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 in bonds.
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?
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?
1.6 Atomic Orbitals

Common elements and their electron
configurations

1.6 Atomic Orbitals

What are the rules that govern our placement
of electrons ?
1.7 Valence Bond Theory

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

bond
1.7 Valence Bond Theory

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

of their time?
1.8 Molecular Orbital Theory

Atomic orbital
wavefunctions overlap to
form 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 be equal to
the number of AOs that
1-29
H2 MOs

Why is the antibonding orbital higher in
energy?
When the AOs overlap, why do the electrons

go into the bonding MO rather than the
antibonding MO?
1-30

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
In general, if a molecule has all of its bonding
molecular form?
and antibonding MOs occupied, will it be
stable or unstable?
Consider TWO of the many MOs that exist for

CH3Br
There are many areas of atomic orbital overlap
Notice how the MOs extend over the entire
molecule
Each picture below represents ONE orbital.
How many electrons can fit into the areas

represented?
In the ground state, electrons occupy some
MOs and not others, WHY?
Depending on the circumstances, we will use

both MO and valence bond theory to explain
phenomena
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?

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?

Orbitals
The carbon must undergo hybridization to
form 4 equal atomic orbitals
The atomic orbitals must be equal in energy
to form four equal-energy symmetrical C-H
bonds

Orbitals
Should the shape of an sp3 orbital look more

like an s or more like p orbital?

Orbitals
To make CH , the 1s atomic orbitals of four H
4
atoms will overlap with the four sp3 hybrid

atomic orbitals of C

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.
Practice with conceptual checkpoint 1.19

1-39

Orbitals
Consider ethene (ethylene).
Each carbon in ethene must bond to three
other atoms, so only three hybridized atomic
orbitals are needed

Orbitals
An sp2 hybridized carbon will have three

equal-energy sp2 orbitals and one
unhybridized p orbital
Which is lower in energy, the sp2 or the p?

1-41
Why?

Orbitals
The sp2 atomic orbitals overlap to form sigma

() bonds
Sigma bonds provide maximum HEAD-ON

overlap

Orbitals
The unhybridized p orbitals in ethene form pi
() bonds, SIDE-BY-SIDE overlap
Practice with conceptual checkpoint 1.20


Orbitals
The unhybridized p orbitals in ethene form pi
() bonds, SIDE-BY-SIDE overlap of p-orbitals
giving both CONSTRUCTIVE and
MO
DESTRUCTIVE
interference
theory
shows the
orbitals that
result.
Remember,
red and
blue regions
are all part
of the same
orbital

Orbitals
Why is sp2 hybridization not appropriate for

methane (CH4)?

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

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
Practice with
SkillBuilder 1.7

Orbitals
Which should be stronger, a pi bond or a
sigma bond? WHY?
Which should be longer, an sp3 sp3 sigma

bond overlap or an sp sp sigma bond
overlap?

Orbitals
Explain the different strengths and lengths
below.
Practice
with
conceptual
checkpoint
1.24
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
1.10 Molecular Geometry

Valence shell electron pair repulsion (VSEPR
theory)
Valence electrons (bonded and lone pairs) repel
each other
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
1.10 sp3 Geometry

For any sp3 hybridized atom, the 4 valence
electron pairs will form a tetrahedral
geometry
electron
The bond
How
Methane group
does
has 4 equal
bonds, so
the bond
angles are
equal
the lone
pair of
ammonia
affect its
geometry?
angels in
oxygen are
even
smaller,
why?
1.10 sp3 Geometry

The molecular geometry is different from
the electron group geometry. HOW?
1.10 sp2 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?
1.10 sp2 Geometry

How many electrons are in Borons
unhybridized p orbital?
Does this geometry follow VSEPR theory?
1.10 sp2 Geometry

Analyze the steric number, hybridization,
electron group geometry and molecular
geometry for this imine?
1.10 sp Geometry
Analyze the Steric number, the hybridization,
the electron group geometry, and the
molecular geometry for the following
molecules
BeH2
CO2
1.10 Geometry Summary

Practice
with
SkillBuilder
1.8
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 esu is a unit of charge. 1 e- has a charge of
4.80 x 10-10 esu
cm are included in the unit, because the distance
Klein, Organic
Chemistry 2e
between the centers of + and charges
affects

Consider the dipole for CH3Cl
Dipole moment () = charge (e) x distance
Plug in the charge and distance
(d)
= (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

Convert to debye
= 1.87 D

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
1-61
mostly covalent?

Check out the polarity of some other
common bonds

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

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

It is important to determine a molecules
geometry FIRST before analyzing its polarity
If you have not drawn the molecule with the
proper geometry, it may cause you to assess
the polarity wrong as well
Would the dipole for water be different if it
were linear rather than angular?

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

Explain why the dipole moment for pentane

=0D
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
Dipole-dipole interactions
Hydrogen bonding
Dispersion forces (a.k.a. London forces or fleeting
dipole-dipole forces)
1.12 Dipole-Dipole
Dipole-dipole forces result when polar
molecules line up their opposite charges.
Note acetones permanent dipole results from
the difference in electronegativity between C
and O
The dipole-dipole attractions BETWEEN
acetone molecules affects acetones boiling
and melting points. HOW?
1.12 Dipole-Dipole
Why do isobutylene and acetone have such
different MP and BPs?
1.12 Hydrogen Bonding

Hydrogen bonds are an especially strong type
of dipole-dipole 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?

Only when a hydrogen shares electrons with
a highly electronegative atom (O, N, F) 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

Which of the following solvents are protic
(capable of H-bonding), and which are not?
Acetic acid
Diethyl ether
Methylene chloride (CH2Cl2)
Dimethyl sulfoxide

Explain why the following isomers have
different boiling points

H-bonds are among
the forces that
cause DNA to form
a double helix and
some proteins to
fold into an alphahelix
1.12 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

Forces
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

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

But like any weak attraction, if there are
enough of them, they can add up to a lot

Forces
The greater the surface area of a molecule,
the more temporary dipole attractions are
possible
Consider the feet of Gecko. They have many
flexible hairs on their feet that maximize
The resulting London dispersion
surface contact
forces are strong enough to support
the weight of the Gecko

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


Forces
Explain why more highly branched molecules
generally have lower boiling points
1.13 Solubility
We use the principle, like-dissolves-like
Polar compounds generally mix well with
other polar compounds
If the compounds mixing are all capable of Hbonding and/or strong dipole-dipole, 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
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
1.13 Solubility
Soap molecules organize into micelles in
water, which form a nonpolar interior to carry
away dirt.
1.13 Solubility
Which attraction is generally stronger?
The attraction between a permanent dipole and
an induced dipole
versus
The attraction between a temporary dipole and an
induced dipole
Which attraction is generally stronger?

The attraction between a polar molecule and a
nonpolar molecule
versus
The attraction between two nonpolar molecules?
1.13 Solubility
Why wont a nonpolar compound readily
dissolve in water?
Is it because the water molecules repel the
nonpolar molecules?
Additional Example
Problems
Draw the structure for C Cl N
2
Draw the structure for CH2O
Draw the structure for CH2O2

Additional Example
Problems
Give all formal charges in the structures
below.
Additional Example
Problems
How many nodes are in the 3s subshell?
How many nodes are in a typical sigma
antibonding MO?
How many nodes are in a typical sp3 orbital?
How many nodes are in a typical pi bonding
MO?
How many nodes are1-90
in a typicalKlein,
pi Organic Chemistry 2e
Additional Example
Problems
Analyze the geometry, polarity and types of
intermolecular attractions for the following
molecules.

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Organic Chemistry

Klein, Organic Chemistry 2e

1.1 Organic Chemistry

The BIG question: WHY do reactions occur?

Klein, Organic Chemistry 2e

1.1 Organic Chemistry

Why are organic compounds important?

Klein, Organic Chemistry 2e

1.2 Structural Theory

What term do we use to describe different

Klein, Organic Chemistry 2e

1.2 Structural Theory

Practice with SkillBuilder 1.1

Klein, Organic Chemistry 2e

1.3 Covalent Bonding

Klein, Organic Chemistry 2e

1.3 Covalent Bonding

What forces keep the bond at the optimal

Klein, Organic Chemistry 2e

1.3 Atomic Structure

1.3 Counting Valence

Klein, Organic Chemistry 2e

1.3 Simple Lewis Structures

Take NH3, for example

Practice with SkillBuilder 1.3

Klein, Organic Chemistry 2e

1.3 Simple Lewis Structures

Try drawing the structure for C2H2

Klein, Organic Chemistry 2e

1.4 Formal Charge

Klein, Organic Chemistry 2e

1.4 Formal Charge

Consider the formal charge example below.

Carbon should have 4 valence electrons,

1.4 Formal Charge

Analyze the formal charge of the oxygen

1.5 Polar Covalent Bonds

Covalent bonds are electrons pairs that exist

Klein, Organic Chemistry 2e

1.5 Polar Covalent Bonds

Covalent bonds are either polar or nonpolar

Electronegativity - how strongly an atom

Klein, Organic Chemistry 2e

1.5 Polar Covalent Bonds

Electrons tend to shift away from lower

The greater the difference in

Klein, Organic Chemistry 2e

1.5 Polar Covalent Bonds

Practice with SkillBuilder 1.5

Klein, Organic Chemistry 2e

1.6 Atomic Orbitals

General Chemistry review

Klein, Organic Chemistry 2e

1.6 Atomic Orbitals

General Chemistry review

Klein, Organic Chemistry 2e

1.6 Atomic Orbitals

Klein, Organic Chemistry 2e

1.6 Atomic Orbitals

In this p-orbital, there is a

Klein, Organic Chemistry 2e

1.6 Atomic Orbitals

Klein, Organic Chemistry 2e