Chapter 1

Electrons, Bonds,
and Molecular
Properties

Suggested Problems -

CHE2201, Chapter 1
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Carbon Compounds Are Ubiquitous

• Living things are

made of organic
chemicals
• Proteins – hair,
cell structures
• Nucleic Acids -
genetic make-up
• Carbohydrates &
fats - energy
• Medicines
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 What Makes Carbon So Special?

• Atoms to the left of carbon give up electrons.

• Atoms to the right of carbon accept electrons.
• Carbon shares electrons.
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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.
– Despite having the same molecular formula some
molecules are not the same
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

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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?

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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
electron by analyzing the electronic configuration.
• For main group elements, just look at the Group
number on the periodic table
• (Group number = # of valence 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.

• Take NH3, for example…

• Note the nitrogen has a lone pair of electrons CHE2201, Chapter 1

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 1.3 Simple Lewis Structures

• Draw the 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.

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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 CHE2201, Chapter 1
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 When two atoms form a bond, one critical consideratio
1.5 Polar Covalent Bonds
What is the dif erence in the electronegativity values of the t
guidelines:
If the dif erence in electronegativity is less than 0.5, t
• There are three equally
types of bonds:
shared between the two atoms, resulting in a covalent b
C− H :
COVALENT BOND: electrons shared between
C C C H
two atoms, where electronegativity difference is
less than 0.5

POLAR COVALENT BOND: electrons shared

between two atoms with electronegativity
dd 9difference 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. CHE2201, Chapter 1
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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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 1.6 Atomic Orbitals
• 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
• 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 Atomic Orbitals
• Electrons behave as both particles and waves.

• The wave theory does match experimental data, and it

has predictive capability.
– Like a wave on a lake, an electron’s wavefunction can be (+), (-),
or ZERO.

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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 CHE2201, Chapter 1
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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 are 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 CHE2201, Chapter 1
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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 CHE2201, Chapter 1
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 1.8 Molecular Orbital Theory
• Imagine a He2 molecule. How would its MOs compare to
those for H2?

• 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, it will be unstable.
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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 CHE2201, Chapter 1
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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

• Sigma bonds provide maximum HEAD-ON overlap

• 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

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The Carbons in Ethane are sp3

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The Carbons in Ethene are sp2

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The Carbons in Ethyne are sp

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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 Hybridized Atomic Orbitals
• Explain the different 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 sp3 Geometry
• 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 sp3 Geometry
• 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 sp2 Geometry
• 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 sp2 Geometry
• 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 sp 2 Geometry
Analyze the steric number, hybridization, electron group
geometry and molecular geometry for this imine?

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

• Consider BeH2

the Be atom has two single 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 Geometry Summary

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 1.11 Molecular Polarity & Dipoles
• Electronegativity differences result in polar bonds
• Induction (shifting of electrons WITHIN their orbitals)
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
• 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
• 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
• 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
• Electrostatic potential maps are often used to give a
visual depiction of polarity

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 1.11 Molecular Polarity

• Explain why the dipole moment for pentane = 0 D

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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 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 affects acetone’s boiling and melting points.

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 1.12 Dipole-Dipole
• 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

acetic acid diethyl ether

(protic) (aprotic)

dimethylsulfoxide, called DMSO

(aprotic)

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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 CHE2201, Chapter 1
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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
instantaneous 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

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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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