KLEIN Chap 1 Handout

1/9/2015
Chapter 1 Structural Theory
1.2 Structural Theory
In the mid 1800s, it was first suggested that substances

are defined by a specific arrangement of atoms.
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:
Why is a compounds formula NOT adequate to define it?
What term do we use to describe different substances

with the same formula?
Practice with SKILLBUILDER 1.1.

Copyright 2012 John Wiley & Sons, Inc.
1-1
Klein, Organic Chemistry 1e
1.3 Covalent Bonding

How do potential energy and stability relate?
1-2
1.3 Covalent Bonding 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:
What forces keep the bond at the optimal

length?
1-3

1-4
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1.4 Formal Charge

Consider the formal charge example below. Calculate the formal
charge on each atom.
or
1.5 Polar Covalent Bonds

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
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.
1-5
1.5 Polar Covalent Bonds

Electrons tend to shift away from lower
electronegativity atoms to higher electronegativity
atoms.
The greater the difference in electronegativity, the more
polar the bond.
1-7
1-6
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.
1-8
1/9/2015
1.6 Atomic Orbitals

Because they are generated
mathematically from wavefunctions,
orbital regions can also be (-), (+), or
ZERO.
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?
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.
1-9
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?
1-11
1-10
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 be equal to the number
of atomic orbitals that were
used.
1-12
H2 MOs
1/9/2015
1.8 Molecular Orbital Theory

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 it MOs occupied, will it
be stable or unstable?
1-13
1.9 Hybridized Atomic Orbitals

To make CH4, the 1s atomic orbitals of the H atoms will
overlap with the four sp3 hybrid atomic orbitals of C.
H2 MOs
1-14

An sp2 hybridized carbon will have three equal-energy
sp2 orbitals and one unhybridized p orbital.
Consider ethene (ethylene).
Each carbon in ethene must bond to THREE other

atoms, so only THREE hybridized atomic orbitals are
needed.
1-15
1-16
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The sp2 atomic orbitals overlap to form sigma () bonds.
The unhybridized p orbitals in ethene form pi () bonds,

created by SIDE-BY-SIDE orbital overlap.
Sigma bonds provide maximum HEAD-ON

overlap.
1-17
Practice with CONCEPTUAL CHECKPOINT 1.20.

1-18
The sp atomic orbitals overlap HEAD-ON to form sigma

() bonds while the unhybridized p orbitals overlap
SIDE-BY-SIDE to form pi () bonds.
Explain the different strengths and lengths below.
Copyright
Practice
with CONCEPTUAL CHECKPOINT 1.24.
2012 John Wiley & Sons, Inc.
1-19
1-20
1/9/2015
1.10 Molecular Geometry

Valence shell electron pair repulsion (VSEPR theory):

To determine molecular geometry:
Valence electrons (bonded and lone pairs) repel each other.
2. Predict the hybridization of the central atom:
To determine molecular geometry:

1. Determine the steric number.
1-21

sp3 Geometry
For any sp3 hybridized atom, the four valence electron pairs
will form a TETRAHEDRAL ELECTRON GROUP geometry:
Methane has four HOW does the
The bond angles in
equal bonds, so the lone pair of ammonia oxygen are even
bond angles are
affect its geometry? smaller. WHY?
equal.
1-23
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.
1-22

sp3 Geometry
The MOLECULAR geometry is different from the
ELECTRON GROUP geometry. HOW?
Example
Arrangement
Steric
Hybridization of electron
number
pairs
CH4
sp3
Tetrahedral
Tetrahedral
NH3
sp3
Tetrahedral
Trigonal pyramidal
H2O
sp3
Tetrahedral
Bent
1-24
Arrangement of
atoms
(geometry)
1/9/2015

sp2 Geometry

Summary
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?

1-25
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.
1-27
1-26

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
1-28
1/9/2015

Check out the polarity of come other common bonds:
1-29

For molecules with multiple polar bonds, the dipole
moment is the vector sum of all of the individual bond
dipoles.
1-30
Electrostatic potential maps are often used to give a

visual depiction of polarity.

1-31
1-32
1/9/2015
1.12 Intermolecular Forces

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?
1-33

Dipoledipole
Why do isobutylene and acetone have such different
MPs and BPs?
1-34

Hydrogen Bonding

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?
Explain why the following isomers have different boiling

points.
1-35
1-36
1/9/2015

London Dispersion Forces

The result is a fleeting attraction between the two

molecules.
Explain why molecules with more mass generally have

higher boiling points.
Such fleeting attractions are generally weak.

However, like any weak attraction, if there are enough
of them, they can add up to a lot.
1-37

Explain why more highly branched molecules generally
have lower boiling points.
1-38
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 H-bonding 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.
1-39
1-40
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1/9/2015

Chapter 1 Structural Theory

1.2 Structural Theory

In the mid 1800s, it was first suggested that substances

Atoms that are most commonly bonded to carbon

Why is a compounds formula NOT adequate to define it?

What term do we use to describe different substances

Practice with SKILLBUILDER 1.1.

Klein, Organic Chemistry 1e

1.3 Covalent Bonding

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

1.3 Covalent Bonding Simple Lewis

Take NH3, for example:

What forces keep the bond at the optimal

Klein, Organic Chemistry 1e

Practice with SKILLBUILDER 1.3.

Klein, Organic Chemistry 1e

1.4 Formal Charge

1.5 Polar Covalent Bonds

Carbon SHOULD have 4 valence electrons because it is in Group IVA on the

Klein, Organic Chemistry 1e

1.5 Polar Covalent Bonds

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

1.6 Atomic Orbitals

The theory does match experimental data, and it has predictive

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

1.6 Atomic Orbitals

1.6 Atomic Orbitals

The sign of the wave function has nothing

In this p-orbital, there is a nodal plane.

Klein, Organic Chemistry 1e

1.7 Valence Bond Theory

Where do the bonded electrons spend most of their

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

1.8 Molecular Orbital Theory

Klein, Organic Chemistry 1e

1.8 Molecular Orbital Theory

1.9 Hybridized Atomic Orbitals

Klein, Organic Chemistry 1e

1.9 Hybridized Atomic Orbitals

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

1.9 Hybridized Atomic Orbitals

Consider ethene (ethylene).

Each carbon in ethene must bond to THREE other

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

Copyright 2012 John Wiley & Sons, Inc.

Klein, Organic Chemistry 1e

1.9 Hybridized Atomic Orbitals

1.9 Hybridized Atomic Orbitals

The sp2 atomic orbitals overlap to form sigma () bonds.

The unhybridized p orbitals in ethene form pi () bonds,

Sigma bonds provide maximum HEAD-ON

Klein, Organic Chemistry 1e

1.9 Hybridized Atomic Orbitals

Practice with CONCEPTUAL CHECKPOINT 1.20.