ORGANIC CHEMISTRY

CHEM 213

Definition

Historically: The molecules that came from

living things.

Thought to have a vital force: Vitalism theory.

Should be impossible to convert inorganic
materials into organic materials.
1828: First organic molecule synthesized from
inorganic materials: Urea

Modern: The Study of Carbon containing

molecules and their reactions.

Synthesis of Urea
O
NH4OCN

H eat

How is this possible?

C
H2N

NH2

Organic Chemistry

What happens to a molecule during a

reaction?

A collision
Bonds break/form

WHAT is a bond?

The BIG question: HOW do reactions

occur?

We will need at least 2 semesters of your

time to answer this question.
Spoiler: FOCUS on the electrons.

Structural Theory

Substances are defined by a specific

arrangement of atoms.

Molecular formula is not sufficient!

Molecular Formula C2H6O => But more than

one arrangement.

Structural Theory

What term do we use to define molecules

with the same molecular formula but
different arrangements?
CONSTITUTIONAL

ISOMERS

Structural Theory

Some common molecules found in organic

molecules makes standard number of bonds

Covalent Bonding

Pair of electrons shared between two elements

Lowest Energy = Most Stable

Valence Electrons

Electrons in the outermost shell of the

atom.

They are the source of:

All Bonding
All Reactions
All your miseries

Valence Electrons

Determining the number of valence electrons

is easy.

Lewis Dot Structure

For simple Lewis structures:

1.

2.

Draw the individual atoms using dots to

represent the valence electrons.
Put the atoms together so they share PAIRS of
electrons to make complete octets. WHAT is an
octet?

Take NH3, for example:

Formal Charge

Formal Charges affect the stability and

reactivity of an atom / molecule and must
therefore be analyzed.
Calculation:

Charge = #of electron the atoms SHOULD

have - # electrons the atoms ACTUALLY has.
Charge = #valence electrons (#bonds)
2*(#lone pairs) (#radicals)

Formal Charge

Rapid Identifications for C, N and O.

Compare to the normal number of bonds for
those elements.

+1 bond = Formal Charge +1

-1 bond = Formal Charge -1

Polar Covalent Bond

Covalent Bonds are either polar or non

polar.

Non polar: Electrons of the bonds are shared

equally
Polar: One of the elements attract the
electrons more

Quantified using electronegativity.

The ability to attract electrons within a bond

Polar Covalent Bond

Electrons shifts within the bonds toward the

element with the highest electronegativity.

The greater the difference in electronegativity

the more polar the bond.

Polar Covalent Bond

Quantification: the difference between the

two electronegativities determine the type
of bond.

< 0.5 covalent

0.5< < 1.7 polar covalent
1.7 < ionic

The Theories of Bonding

Atomic Orbitals

Orbital can be identified

by its shape.

Orbital: region where

there is a calculated 90%
probability of finding an
electron.

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.

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.

Atomic Orbitals

Electrons are most stable (lowest in energy) if they

are in the 1s orbital?

Atomic Orbitals

Once the 2s is full, electrons fill into the three

DEGENERATE 2p orbitals.

Electron Configuration

Valence Bond Theory

A bond occurs when atomic orbitals overlap.

Overlapping orbitals are like overlapping waves.

Only constructive interference results in a bond.

Valence Bond Theory

The bond for an H2 molecule results from

constructive interference.

Where do the bonded electrons spend most of their

time?

Molecular Orbital Theory

Molecular Orbitals (MOs)

that extend over the entire
molecule.
MOs include both
constructive and
destructive interference.
Number of MOs = Number
of AO

H2 MOs

Molecular Orbital Theory

Antibonding orbital is
higher in energy.

When the atomic orbitals

overlap, the electrons go
into the bonding MO
rather than the
antibonding
MO.

H2 MOs

Molecular Orbital Theory

Construct the MO diagram

for He2?

How would the energy of

the He2 compare to 2 He?

Conclude on the Existence

of He2.

H2 MOs

Molecular Orbital Theory

Consider the MOs for CHBr3:

There are many areas of atomic orbital overlap.

Notice how the MOs extend over the entire molecule.
Each picture represents ONE orbital.

Molecular Orbital Theory

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.

Hybridized Atomic Orbitals

Given the electron

configuration for C
and H, imagine how
their atomic orbitals
might overlap.

Would such orbital

overlap yield
methane?

Hybridized Atomic 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?

Hybridized Atomic 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.

Hybridized Atomic Orbitals

Should the shape of an sp3 orbital look more like an

s or more like p orbital?

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.

Hybridized Atomic Orbitals

Consider ethene (ethylene).

Each carbon in ethene must bond to THREE other

atoms, so only THREE hybridized atomic orbitals are
needed.

Hybridized Atomic Orbitals

An sp2 hybridized carbon will have three equalenergy sp2 orbitals and one unhybridized p orbital.

Hybridized Atomic Orbitals

The sp2 atomic orbitals overlap to form sigma ()

bonds.

Sigma bonds provide maximum HEAD-ON

overlap.

Hybridized Atomic Orbitals

The unhybridized p orbitals in ethene form pi ()

bonds, created by SIDE-BY-SIDE orbital overlap.

Hybridized Atomic Orbitals

Why is sp2 hybridization not appropriate for methane

(CH4)?

Hybridized Atomic Orbitals

Consider ethyne (acetylene).

Each carbon in ethyne must bond to TWO other

atoms, so only TWO hybridized atomic orbitals are
needed

Hybridized Atomic 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.

Bond Length / Strength

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.

Molecular Geometry

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.

Molecular Geometry: sp3

For any sp3 hybridized atom, the four valence electron

pairs will form a TETRAHEDRAL ELECTRON GROUP
geometry:

HOW does the

Methane has four
equal bonds, so the lone pair of
bond angles are
ammonia affect its
equal.
geometry?

The bond angles

in oxygen are even
smaller. WHY?

Molecular Geometry: sp3

The MOLECULAR geometry is different from the

ELECTRON GROUP geometry. HOW?

Example

Arrangement
Steric
Hybridization of electron
number
pairs

Arrangement
of atoms
(geometry)

CH4

sp3

Tetrahedral

Tetrahedral

NH3

sp3

Tetrahedral

Trigonal
pyramidal

H2O

sp3

Tetrahedral

Bent

Molecular Geometry: sp2

Calculate the steric number for BF3.

Electron pairs that are located in sp2 hybridized

orbitals will form a trigonal planar ELECTRON
GROUP geometry.

Molecular Geometry

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.

Molecular Polarity

Dipole for C-Cl bond is 1.87 D

What would the dipole moment be if CH3Cl were
100% ionic?

= charge (e) x distance (d)

= (4.80 x 10-10 esu) x (1.772 x 10-8 cm)

Plug in the charge and distance

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?

Molecular Polarity

Molecular Polarity

For molecules with multiple polar bonds, the dipole

moment is the vector sum of all of the individual
bond dipoles.

Molecular Polarity

Electrostatic potential maps are often used to give a

visual depiction of polarity.

Molecular Polarity

Intermolecular Forces
(IMF)

Attractions BETWEEN molecules are responsible for:

Solubility
Boiling points / melting points
Density

Neutral molecules (polar and nonpolar) are attracted

to one another through:

Dipoledipole interactions
Hydrogen bonding
Dispersion forces (a.k.a. London forces or fleeting dipole
dipole forces)

IMF: Dipole Dipole

Dipoledipole forces result when polar molecules line

up their OPPOSITE charges.

IMF: H-Bonding

Hydrogen bonds (H-bonds) are an especially strong

type of dipoledipole attraction.

IMF: H-Bonding

The H MUST be bonded to a N, O or F and interacts

with another N, O or F.
H-bonds are about 20 times weaker than covalent
bonds.
Compounds with H atoms that are capable of
forming H-bonds are called PROTIC.

IMF: London Dispersion

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.

IMF: London Dispersion

Forces

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.

IMF: London Dispersion

Forces

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.

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.

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.

Solubility

Soap molecules organize into micelles in water,

which form a nonpolar interior to carry away dirt.

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?