Organic Chemistry

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
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 Klein, Organic Chemistry 2e
1.1 Organic Chemistry
Whler, 1928
1.2 Structural Theory
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.
Some electrons are close to the nucleus and others are far
away.
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 e- configuration.
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
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 has balance out the 4 it should have, so
it does not have formal charge. Its neutral.
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 it should only have 6, what is its
formal charge?
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 H2 MOs
must be equal to the number
of AOs that were used.
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?
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?
In general, if a molecule has all of its bonding 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?
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?
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
Should the shape of an sp3 orbital look more like an s or

more like p orbital?
To make CH4, the 1s atomic orbitals of four H atoms will
overlap with the four sp3 hybrid atomic orbitals of C
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
Consider ethene (ethylene).
Each carbon in ethene must bond to three other atoms,

so only three hybridized atomic orbitals are needed
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? Why?
The sp2 atomic orbitals overlap to form sigma () bonds
Sigma bonds provide maximum HEAD-ON overlap
The unhybridized p orbitals in ethene form pi () bonds,
SIDE-BY-SIDE overlap
Practice with conceptual checkpoint 1.20
The unhybridized p orbitals in ethene form pi () bonds,
SIDE-BY-SIDE overlap of p-orbitals giving both
CONSTRUCTIVE and DESTRUCTIVE interference
MO theory
shows the
orbitals that
result.
Remember, red
and blue
regions are all
part of the
same orbital
Why is sp2 hybridization not appropriate for methane

(CH4)?
Consider ethyne (acetylene).
Each carbon in ethyne must bond to two other atoms, so

only two hybridized atomic orbitals are needed
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
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?
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 sp 3 Geometry
For any sp3 hybridized atom, the 4 valence electron pairs
will form a tetrahedral electron group geometry
Methane has 4 How does the The bond
equal bonds, lone pair of angels in
so the bond ammonia oxygen are
angles are affect its even smaller,
equal geometry? why?
1.10 sp 3 Geometry
The molecular geometry is different from the electron
group geometry. HOW?
1.10 sp 2 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 sp 2 Geometry
How many electrons are in Borons unhybridized p
orbital?
Does this geometry follow VSEPR theory?
1.10 sp 2 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 between the
centers of + and charges affects the dipole
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
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 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 = 0 D

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 alpha-helix
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
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
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
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 surface contact
The resulting London dispersion forces are
strong enough to support the weight of the
Gecko
Explain why molecules with more mass generally have
higher boiling points
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 H-bonding 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 C2Cl3N
Draw the structure for CH2O
Draw the structure for CH2O2
Give all formal charges in the structures below.
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 are in a typical pi antibonding MO
Analyze the geometry, polarity and types of
intermolecular attractions for the following molecules.

Organic Chemistry

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Organic Chemistry

Hochgeladen von

Copyright:

Verfügbare Formate

Organic Chemistry

The BIG question: WHY do reactions occur?

Practice with SkillBuilder 1.1

What forces keep the bond at the optimal length?

Look at carbon for example. Which electrons are the valence

Why are valence electrons important?

Practice with SkillBuilder 1.2

Practice with SkillBuilder 1.3

Carbon should have 4 valence electrons, because it is in

Oxygen should have 6 valence electrons, because it is in

Just like an atomic orbital, the electrons could be

What factors determine which atom in the bond will

The greater the difference in electronegativity, the more

Practice with SkillBuilder 1.5

Practice with SkillBuilder 1.6

Only constructive interference results in a bond

Where do the bonded electrons spend most of their

When the AOs overlap, why do the electrons go into the

Why does Helium exist in its

Depending on the circumstances, we will use both MO

Would such orbital overlap

If four H atoms were to come in and overlap with the 2s

Should the shape of an sp3 orbital look more like an s or

Draw a picture that shows the necessary atomic orbitals

Practice with conceptual checkpoint 1.19

Each carbon in ethene must bond to three other atoms,

Which is lower in energy, the sp2 or the p? Why?

Sigma bonds provide maximum HEAD-ON overlap

Practice with conceptual checkpoint 1.20

Why is sp2 hybridization not appropriate for methane

Each carbon in ethyne must bond to two other atoms, so

Which should be longer, an sp3 sp3 sigma bond overlap

Practice with SkillBuilder 1.9

Explain why the dipole moment for pentane = 0 D

Methylene chloride (CH2Cl2)

Nonpolar molecules normally have their electrons ()

However, the electrons are in constant random motion

Such fleeting attractions are generally weak.

Practice with SkillBuilder 1.10

Which attraction is generally stronger?

Draw the structure for CH2O

Draw the structure for CH2O2

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 are in a typical pi antibonding MO

Das könnte Ihnen auch gefallen