Organic Chemistry

Third Edition
David Klein

Chapter 1
A Review of General Chemistry: Electrons, Bonds,
and Molecular Properties
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 1.1 Organic Chemistry
• The study of carbon-containing molecules and their reactions
• What happens to a molecule during a reaction?
– molecules collide
– bonds are broken and bonds are made

• Why do reactions, like the one above, occur?

– We will need at least 2 semesters of your time to answer
this question
– FOCUS ON THE ELECTRONS

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 1.1 Organic Chemistry
• Why do we distinguish between organic and inorganic
compounds?

Organic compounds contain carbon atoms

• Why are organic compounds important? Organic compounds

make up things like:
- Food
- Clothes
- Pharmaceuticals
- Plastics

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 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?
Because compounds differ in the specific ways in which
atoms are bonded together

• Compounds with the same molecular formula but different

structures are constitutional isomers.

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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

• Practice with SkillBuilder 1.1

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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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 1.3 Covalent Bonding
• How do potential energy and stability relate?

• What forces keep the bond at the optimal length?

- Attractive forces between positively charged nuclei and negatively
charged electrons
- Repulsive forces between the two positively charged nuclei
- Repulsive forces between the two negatively charged electrons

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 1.3 Atomic Structure
• A review from General Chemistry
– Protons (+1 charge) and neutrons (neutral) reside in the
nucleus
– Electrons (-1 charge) reside in orbitals outside the nucleus.

– Valence electrons are the electrons in the outermost shell

– Look at carbon for example. Which electrons are the valence

electrons?

– Valence electrons are our focus: because they involved in

bonding!
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 1.3 Counting Valence Electrons
• You can always calculate the number of valence electrons by
analyzing the e- configuration.
• Or, for Group A elements only, just look at the Group number on
the periodic table (Group number = # of valence electrons)

• Practice with SkillBuilder 1.2

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 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.

• Take NH3, for example…

• Note the nitrogen has a lone pair of electrons

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 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.

• Skillbuilder 1.3: Try drawing a Lewis structure for CH2O

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 1.4 Formal Charge
• Recall the terms we use to describe atoms with an unbalanced or
FORMAL charge.
Anion = negatively charged atom
Cation = positively charged atom

• Atoms in molecules (sharing electrons) are typically neutral, but

can also be anionic or cationic

• To to determine the formal charge for an atom in a given

molecule, compare the number of valence electrons that it owns
(based on its bonding pattern) to the number of valence electrons
that the atom needs to be neutral.

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 1.4 Formal Charge
• Consider the formal charge on the atoms in the structure below,
and determine if any of the atoms should have a formal charge

• Carbon needs 4 valence electrons to be neutral (Group IV)

• Carbon is surrounded by 8 electrons here, but it only owns 4 of
them (1 from each of the bonds).
• Since carbon owns 4 electrons, and needs 4 electrons to be
neutral, it does not have a formal charge.

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 1.4 Formal Charge
• Now determine if the oxygen atom has a formal charge here.

We need to write a
negative charge next
to the oxygen atom

• Oxygen needs 6 valence electrons to be neutral (Group VI)

• Oxygen is surrounded by 8 electrons here, but it only owns 7 of
them (1 from the bond, plus 3 lone pairs ).
• Since oxygen owns 7 electrons here, and needs 6 electrons to be
neutral, it has an extra electron, and therefore has a -1 charge.

• Practice with SkillBuilder 1.4

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 1.5 Polar Covalent Bonds
• Electronegativity - how strongly an atom attracts shared electrons

• If you remember that F is the most electronegative atom, then

you can always remember the relative electronegativity of the
atoms in the same column or the same row of the PTE

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 1.5 Polar Covalent Bonds
• There are three types of bonds:

COVALENT BOND: electrons shared between

two atoms, where electronegativity difference is
less than 0.5

POLAR COVALENT BOND: electrons shared

between two atoms with electronegativity
difference between 0.5 and 1.7

IONIC BOND: the electrons are not really shared,

the two atoms differ in electronegativity by
more than 1.7, and so the more electronegative
atom owns the electrons.
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 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.

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 1.5 Polar Covalent Bonds
• Some bonds are acceptable to write as a covalent bond or an ionic
bond, as in the following example:

• The electronegativity difference is 1.5, so it is on the cusp of polar

covalent and ionic, according to just one method used for
determining electronegativity values. So, the absolute difference
in electronegativity is to be taken with a grain of salt.

• Practice with SkillBuilder 1.5

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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 are wave functions; The 3D plot

of a (wave function)2 gives an image of an atomic orbital

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 1.6 Atomic Orbitals = Electron Density
• The type of orbital is identified by its shape (s, p)

• Electron density: term used to refer to probability of finding an

electron (the orbital shape is 90-95% of the space where an
electron “probably” is)

• We think of an atomic orbital as a cloud of electron density

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 1.6 Phases of 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 electron’s wavefunction can have a
positive (+) value, a negative (–) value, or zero (a node).

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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 in 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, like every atomic orbital, can have up to 2 electrons
in it. If there are more electrons in the atom they fill up the 2s
the 2p orbitals

The 2p orbitals are of equal

energy, and thus are
degenerate orbitals

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 1.6 Atomic Orbitals
Common elements and their electron configurations

• The placement of electrons are governed by the following: Aufbau

principle, Pauli exclusion principle, and Hund’s Rule

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 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

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 1.7 Valence Bond Theory
• The bond for a H2 molecule results from constructive interference

direct overlap of orbitals

forms a sigma bond

• The bonded electrons spend most of their time in the overlapping

atomic orbital space… which is called a sigma (s) bond

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 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 Molecular Orbitals for H2

must be equal to the number of
AOs that were used.

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 1.8 Molecular Orbital Theory
• The antibonding MO has higher energy because it has one node.

• When the AOs overlap the electrons go into the bonding MO

rather than the antibonding MO in order to achieve a lower
energy state
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 1.8 Molecular Orbital Theory
• The are more than two MOs that exist for CH3Br.. But let’s focus on
only two of them here
– There are many areas of atomic orbital overlap, and nodes as
well
– Notice how the MOs extend over the entire molecule

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 1.8 Molecular Orbital Theory
• Each MO can hold two electrons?
• In the ground state, electrons occupy lower energy MO’s while the
higher energy ones remain unoccupied

• These two MO’s here are the most important ones: The highest
occupied MO (HOMO) and the lowest unoccupied MO (LUMO)
• These are the MO’s in play when undergoing a chemical rxn

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 1.9 Hybridized Atomic Orbitals
• the ground state electron configuration for carbon can’t explain
how carbon makes four bonds

Only two orbitals have unpaired There are 4 unpaired electrons

electrons to be shared in the here, but 4 equal bonds cannot
ground state be made with two different
types of orbitals (s vs p)

• If considering the excited state, it still doesn’t explain how carbon

makes 4 equivalent bonds, like the 4 bonds to H in a methane
molecule
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 1.9 Hybridized Atomic Orbitals
• The carbon must undergo hybridization to form 4 equal atomic
orbitals, with symmetrical geometry

• The atomic orbitals must be equal in energy to form four equal-

energy symmetrical C-H bonds

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 1.9 Hybridized Atomic Orbitals

• the shape of an sp3 orbital results from have 25% s-character, and
75% p-character

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

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 1.9 Hybridized Atomic 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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 1.9 Hybridized Atomic Orbitals
• An sp2 hybridized carbon will have three equal-energy sp2 orbitals
and one unhybridized p orbital

• the shape of an sp2 orbital results from have 33% s-character, and
67% p-character

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 1.9 Hybridized Atomic Orbitals
• The sp2 atomic orbitals overlap to form sigma (σ) bonds

• The p orbitals, here, overlap to form a pi bond

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 1.9 Hybridized Atomic Orbitals
• The pi (π) bond is formed by SIDE-BY-SIDE overlap of the p
orbitals. The electron density of the pi bond is spread out above
and below the plane of the molecule, as shown below

• Pi bonds are weaker than sigma bonds.

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 1.9 Hybridized Atomic Orbitals
• The pi bond is described in a similar way according to MO theory.

Remember, red and

blue regions are all
part of the same
orbital, but opposite
phases

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 1.9 Hybridized Atomic 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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 1.9 Hybridized Atomic Orbitals
• The sp atomic orbitals overlap HEAD-ON to form sigma (σ) bonds
while the unhybridized p orbitals overlap SIDE-BY-SIDE to form pi
bonds

• Practice with Skillbuilder 1.7

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 1.9 Bond Strength and Length
• Which should be stronger, a pi bond or a sigma bond?

The sigma bond is considered stronger as it requires almost twice

the bond energy of a pi bond to break it

• Which should be longer, an sp3 – sp3 sigma bond overlap or an sp –

sp sigma bond overlap? Realize the more s-character in the
orbitals, the shorter they will be

sp3 bond lengths are the longest, followed by sp2, and then sp
bonds.
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 1.9 Bond Strength and Length
• Rationalize the bond strengths and lengths below

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 1.10 Molecular Geometry
• Valence shell electron pair repulsion (VSEPR theory)

Valence electrons (shared and lone pairs) repel each other

• To determine molecular geometry, start with the steric number…

which gives us a quick prediction

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 1.10 Molecular Geometry
• The steric number translate to 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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 1.10 Molecular Geometry – sp3
• For any sp3 hybridized atom, the 4 valence electron pairs will form
a tetrahedral electron group geometry
• Methane has 4 • The bond angles • The bond angles
equal bonds, so in ammonia are a in oxygen are
the bond angles little smaller even smaller still
are equal

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 1.10 Molecular Geometry – sp3
• The molecular geometry is described for only the atoms bonded
to the central atom; electron group geometry includes lone pairs

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 1.10 Molecular Geometry – sp2
• Calculate the steric number for BF3

• The electron pairs in sp2 hybridized orbitals (either bonded

electrons or lone pairs) will form a trigonal planar electron group
geometry (steric number = 3 = trigonal planar)

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 1.10 Molecular Geometry – sp2
• Realize that the boron atom, in BF3, is sp2 hybridized. The three
bonds are made with sp2 orbitals, and the unhybridized p orbital
remains empty

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 1.10 Molecular Geometry – sp
• When steric number = 2, the geometry will be linear and the
atom will be sp-hybridized

• Consider BeH2

the Be atom has two s bonds

using sp orbitals, and two empty
p orbitals

• Draw a Lewis structure for CO2. Are the p orbitals on the C atom
also empty in this compound, like they are with Be in the previous
example?

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 1.10 Molecular Geometry – Summary

• Practice with
SkillBuilder 1.8

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 1.11 Molecular Polarity & Dipoles
• Electronegativity differences result in polar bonds
• Induction (shifting of electrons within an orbital) results in a
dipole moment.

• Dipole moment = (the amount of partial charge) x (the distance

the δ+ and δ- are separated)
• Dipole moments are reported in units of debye (D)

• 1 debye = 10-18 esu ∙ cm

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 1.11 Molecular Polarity & Dipoles
• Consider the dipole for CH3Cl
• Dipole moment (μ) = charge (e) x distance (d)

– Plug in the charge and distance

• μ = (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)
• μ = 1.87 x 10-18 esu ∙ cm
– Convert to debye
• μ = 1.87 D
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 1.11 Molecular Polarity & Dipoles
• What would the dipole moment be if CH3Cl were 100% ionic?
• μ = charge (e) x distance (d)

– Plug in the charge and distance, using

the full charge of an electron

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

• μ = 8.51 x 10-18 esu ∙ cm = 8.51 D

• What % of the C-Cl bond is ionic?
• 22% ionic character means the C-Cl bond is
mostly covalent
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 1.11 Molecular Polarity & Dipoles
• The polarity of some other common bonds

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 1.11 Molecular Polarity & Dipoles
• Why is the C=O double bond so much more polar than
the C-O single bond?

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 1.11 Molecular Polarity & Dipoles
• For molecules with multiple polar bonds, the dipole moment is
the vector sum of all of the individual bond dipoles

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 1.11 Molecular Polarity & Dipoles
• you have to know the molecule’s geometry 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 water have a different dipole moment if it were linear

instead of bent?

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 1.11 Molecular Polarity & Dipoles
• Electrostatic potential maps are often used to give a visual
depiction of polarity

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 1.11 Molecular Polarity & Dipoles

• Practice with SkillBuilder 1.9

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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
separate 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)

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 1.12 Dipole-Dipole Attractions
• Dipole-dipole forces result when polar molecules line up their
opposite charges.

• Note acetone’s permanent dipole results from the difference in

electronegativity between C and O

• The dipole-dipole attractions BETWEEN acetone molecules

increases acetone’s boiling and melting points while similar
molecules without dipole-dipole interactions, such as isobutylene,
have lower boiling and melting points.

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 1.12 Dipole-Dipole Attractions
• Isobutylene and acetone have such different MP and BPs because
of dipole-dipole interactions. Isobutylene lacks a significant
dipole moment.

isobutylene is less polar, has Acetone is more polar, and so it

weaker dipole-dipole attractions has a higher BP
and therefore a lower BP

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 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
• H-bonding is the attractive force between an H bonded to an
electronegative atom (N, O and F) and a lone pair on another
electronegative atom.

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 1.12 Hydrogen Bonding
• Only when a hydrogen shares electrons with a highly
electronegative atom (O, N, F) will it carry a large partial positive
charge

• The large δ+ on the H atom can attract large δ– charges on other

molecules

• Even with the large partial charges, H-bonds are still about 20
times weaker than covalent bonds

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 1.12 Hydrogen Bonding
• Solvents that engage in H-bonding are called protic solvents.
Solvents that do not H-bond are aprotic
O

H2 H2
C C C
H3C OH H3C O CH3
acetic acid diethyl ether
(protic) (aprotic)

S
dimethylsulfoxide, called DMSO
(aprotic)
H3C CH3

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 1.12 Hydrogen Bonding
• Increasing the amount and extent of hydrogen bonding explains
why the following isomers have different boiling points

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 1.12 Hydrogen Bonding

• H-bonds are among the

forces that cause DNA to
form a double helix and
some proteins to fold into
an alpha-helix

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 1.12 London Dispersion Forces
• If two molecules are nonpolar (dipole = 0 D), they still will have an
attractive force between them

– This occurs due to an induced, transient dipole moment, called

London Dispersion Forces

• 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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 1.12 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

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 1.12 London Dispersion 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 be significant

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 1.12 London Dispersion 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 surface contact

• The resulting London dispersion forces are strong

enough to support the weight of the Gecko

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 1.12 London Dispersion Forces
• London dispersion forces are the reason why molecules with more
mass generally have higher boiling points

• Practice with SkillBuilder 1.10

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 1.12 London Dispersion Forces
• The more branching in a molecule, the lower it’s surface area, and
the weaker the London dispersion forces.

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 1.13 Solubility
• As you learned in general chemistry, 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
shouldn’t 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 can’t use just water to wash oil off our dirty cloths

• To remove nonpolar oils, and 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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