Chapter 1 Outline

This first slide presentation will include

review from general chemistry therefore it
will cover more information that in the
textbook.
Periodic table & trends
Ionic & covalent bonding
Atomic structure, orbitals and isotopes
Molecular orbitals and hybridization
Acids/base chemistry

s-block (metals), p-block (non-metals)

An ionic bond is formed between metals

and non-metals

Covalent Bonds are Formed by

Sharing Electrons Between Non-Metals

Nonpolar covalent bond = bonded atoms are the same

No difference in electronegativity between atoms

Polar covalent bond = bonded atoms differ in electronegativity

How Many Bonds Does

an Atom Form?

Lewis Structures

Bond Polarity Depends on

the Difference in Electronegativity

Polar Covalent Bonds

Formal Charge

For example, consider oxygen in methanol shown

below.
Oxygen is in group 16, which means a valence
number of 6.
Oxygen has two lone pairs and shares an
electron in each of the two covalent bonds so
FC = 6 4 (4) = 0

Formal Charge

Methyl oxonium ion (the acidic form of methanol) is shown below.

In this structure, oxygen has used one of its lone pair to form a covalent bond
with a proton so the formal charge for oxygen is
FC = 6 2 (6) = +1

Neutral Carbon Forms Four Bonds

if carbon does not form four bonds, it has a charge

(or it is a radical)

A Hydrogen Atom Can Lose or

Gain an Electron

Neutral Nitrogen Forms Three Bonds

Nitrogen has one lone pair.

If nitrogen does not form three bonds, it is charged.

Neutral Oxygen Forms Two Bonds

Oxygen has two lone pairs.

If oxygen does not form two bonds, it is charged.

Hydrogen and the Halogens

Form One Bond

A halogen has three lone pairs.

if hydrogen or halogen does not form one bond, it has a charge
(or it is a radical)

Lewis Structures

In organic chemistry it is common to use lines to represent covalent bonds.

A single line between atoms represents one bond, two lines represents a double
bond, and three lines represents a triple bond.

Drawing Conventions in Organic Chemistry

Learn to use line/bond drawing convention for Lewis structures

Simplifies drawing task

Atomic & Molecular Orbitals

The Structure of an Atom

Protons are positively charged.
Neutrons have no charge.
Electrons are negatively charged.
Atomic number = # of protons
Atomic number of carbon = 6
Neutral carbon has six protons
and six electrons.

Isotopes
Isotopes are atoms that have the same atomic number (number
of protons) but differ in mass (differing number of neutrons)
Isotopes may be stable or unstable (radioactive).
Isotopes are widely used to understand chemical mechanism and
as radiotracers

stable

Unstable
(beta emitter)

The Distribution of Electrons in an Atom

The first shell is closest to the nucleus.

The closer the atomic orbital is to the
nucleus, the lower its energy.
Within the same shell, s < p.

-Aufbau principle: An electron goes into the atomic orbital with

the lowest energy.
-Pauli exclusion principle: No more than two electrons can be
in an atomic orbital.
-Hunds rule: An electron goes into an empty degenerate
orbital rather than pairing up.

Reorder such that energy becomes the y-axis

Electrons may be excited from lower to higher energy

orbitals creating excited electronic states

What is an Atomic Orbital?

The Lobes of a p Orbital Have

Opposite Phases

The Three p Orbitals

Molecular Orbitals - Diatomic

Hydrogen
Hydrogen is one of the seven elements that form
diatomic molecules. In order for H2 to form, atomic
hydrogen must come together to form a covalent
bond.
Orbital overlap

1s
+
1s
atomic hydrogen

molecular hydrogen

Atomic Orbitals Combine

to Form Molecular Orbitals

Side-to-Side Overlap of In-Phase

p Orbitals Forms a Bond

Molecular Geometry & Hybridization

The Bonding in Methane

In Order to Form Four Bonds,

Carbon Must Promote an Electron

Four Orbitals are Mixed to Form

Four Hybrid Orbitals

An sp3 orbital has a large lobe and a small lobe.

The Carbon in Methane is sp3

4 sp3 orbitals = tetrahedron

.

The Carbon Hydrogen Bond

When the four sp3 hybrid orbitals of carbon
overlap with four 1s orbitals of hydrogen,
tetrahedral geometry arises

The Bonding in Ethane

The Bonding in Ethane

Graphically, the molecular orbitals of ethane can be represented as:

The Bonding in Ethane

Bonding in Ethene

Molecular Orbitals in Ethene

An sp2 Carbon Has Three sp2 Orbitals

and One p Orbital

The Carbons in Ethene are sp2

Bonding in Ethyne

Molecular Orbitals in Ethyne

The Two sp Orbitals Point in Opposite Directions

The Two p Orbitals are Perpendicular

The Carbons in Ethyne are sp

Methyl Cation and Methyl Radical are sp2

Methyl Anion is sp3

Nitrogen Has Three Unpaired Valence Electrons

and Forms Three Bonds in NH3

Nitrogen does not have to promote an electron.

The Bonds in Ammonia (NH3)

The Ammonium Ion (+NH4)

Oxygen Has Two Unpaired Valence

Electrons and Forms Two Bonds in H2O

Oxygen does not have to promote an electron.

The Bonds in Water (H2O)

Overlap of an s Orbital with an sp3 Orbital

The Length and Strength of a

Hydrogen Halide Bond

Summary of Hybridization

orbitals used in bond formation determine the bond angle

Single Bond: 1 Double bond: 1 + 1

Triple Bond: 1 + 2

Hybridization of C, N, and O

Bond Strength and Bond Length

The shorter the bond, the stronger it is.

s Character

The shorter the bond, the stronger it is.

The More s Character in the Orbital,

the Shorter and Stronger the Bond

The more s character, the shorter and stronger the bond.

The More s Character in the Orbital,

the Greater the Bond Angle

The more s character, the greater the bond angle.

Hybridization, Bond Angle,

Bond Length, Bond Strength

Summary
The shorter the bond, the stronger it is.
The greater the electron density in the region of orbital
overlap, the stronger the bond.
The more s character, the shorter and stronger the bond.
The more s character, the larger the bond angle.

A Bond is Weaker Than a Bond

Dipole Moments of Molecules

Dipole Moments of Molecules

Acids and Bases Reactions in Equilibrium

Two acid base theories will be explored:

Bronsted Lowery acid base theory: loss and
gain of a proton
Lewis acid base theory: donation or
acceptance of a pair of electrons

B.L. AcidBase Reactions in Equilibrium

Equilibrium arrows indicate the if the products or

reactants are favored

An Acid Loses a Proton

A Base Gains a Proton

When an acid loses a proton, it forms its conjugate base.

When a base gains a proton, it forms its conjugate acid.

An Acid and its Conjugate Base

A Base and its Conjugate Acid

The stronger the acid, the weaker its conjugate base.

Acids Have Different Strengths

The stronger the acid, the weaker its conjugate base.

Acid Strength

The stronger the acid, the larger the Ka.

The stronger the acid, the smaller the pKa.

See Simple pKa Chart on course

web for a complete list. You must
know pKa values for exams.

Water & Alcohols Can Act as

Either Acid or Base

Alkoxide
anion

Alcohol

Oxoniu
m cation

An Amine Can Behave

as an Acid and as a Base

A curved arrow points from the electron donor to the electron acceptor.

An Amine Can Behave

as an Acid and as a Base

Amide
anion

ammoni
a

Ammoniu
m cation

Other Amine Acid/Base Chemistry

The Position of Equilibrium

Take Home Concept:
The equilibrium favors formation of the weaker acid.

Determine Position of Equilibrium

First Label the acids

Determine Position of Equilibrium

acid

acid

First Label the acids

Second, approximate the pKas

Determine Position of Equilibrium

Acid
35

Acid
15

First Label the acids

Second, approximate the pKas

Determine Position of Equilibrium

Acid
35

Acid
15

First Label the acids

Second, approximate the pKa value
Equilibrium always favors the weaker acid
(larger pKa value)

The Stronger the Acid,

the Weaker Its Conjugate Base

stable bases are weak bases

Why are Alcohols Stronger Acids Than Amines?

Oxygen is more electronegative than nitrogen.

Why Are Protonated Alcohols Stronger Acids

Than Protonated Amines?

Oxygen is more electronegative than nitrogen.

Substituents Affect the

Strength of the Acid

inductive electron withdrawal

HX vs Substituted Acetic Acid Trends

For substituted carboxylic acids, consider the conjugate base forms.
The area circled in red has a lot of excess electron density. Groups near
this electron density can help stabilize it if they are electronegative. Since
Cl is more electronegative than Br, the conjugate base form of 2chloroacetic acid is more stable - therefore the acid is stronger

HX vs Substituted Acetic Acid Trends

Another way to think about it is bond dipoles. Because the singly
bonded oxygen of the carboxylate is negatively charged, that forces the
carbon next to it to be positively charged, which in turn forces the next
carbon to be negatively charged. The more electronegative atom will
stabilize carbon #2 better

pKa 2.81

pKa 2.86

Smaller pKa = stronger acid

Chlorine more electronegative than bromine

pKa ~0

A Substituents Effect on pKa

Depends on Distance

HX vs Substituted Acetic Acid Trends

Comparing acids such as HCl to HI, you can think
about the bond strength. The weaker the bond, the
easier to break.

The Length and Strength of a

Hydrogen Halide Bond
Acid
strength

Base
Base strength

pKa

form

3.14

F-

-7

Cl-

-8

Br-

-9

I-

Why is a Carboxylic Acid a Stronger Acid

Than an Alcohol?
delocalized electrons (resonance)

Lab #1 How ionization impacts solubility

like dissolves like

pKa = ?

pKa = ?

Red is a greasy hydrocarbon (not soluble in water) Blue is the carboxylic

acid functional group (neutral) and Carboxylate (charged)

Can be used to separate

compounds using extraction
techniquies

The HendersonHasselbalch Equation

Lab the week of Sept 7th. In summary, when the pKa of an acid is equal to the
pH of the solution, then there will be 50:50 distribution between ionized and
unionized forms.

Amine-based Drugs are often Salts

A carboxylic acid is neutral in its acidic form and charged in its basic form.
An amine is charged in its acidic form and neutral in its basic form.

Hybridization Affects Acidity

More s
character
most
electronegati
ve

Less s
character
less
electronegati
ve

The weakest acid has the

strongest conjugate base.

Hybridization Affects Acidity

Electron pair
in sp orbital
(more stable)

Electron pair
in sp3 orbital
(less stable)

Lewis Acids and Bases

Lewis definitions:
acid: a species that accepts a share in an electron pair
base: a species that donates a share in an electron pair

All Brnsted acids (proton donor) are Lewis acids.

All Brnsted bases (proton acceptor) are Lewis bases.

Lewis Acids and Bases