Acids and Bases

or general chemistry, analytical and a

whole lot more!

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Reference Book
• Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr

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HISTORY
• By the early 19th century, many acids that do not contain
oxygen were known. By 1838, Liebig defined acids as
"compounds containing hydrogen, in which the hydrogen can
be replaced by a metal,"

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Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

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 A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor

base acid acid base

conjugate conjugate
base acid
acid base

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 Acid-Base Properties of Water

H2O (l) H+ (aq) + OH- (aq)

autoionization of water

+ -
H O + H O [H O H ] + H O
H H H

conjugate
base
acid
H2O + H2O H3O+ + OH-
acid conjugate
base
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Molecular Structure and Acid Strength
H X H+ + X-

The The
stronger weaker
the bond the acid

HF << HCl < HBr < HI

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 Molecular Structure and Acid Strength
d- d+
Z O H Z O- + H+

The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state

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 Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from

the same group and that have the same oxidation number.

Acid strength increases with increasing electronegativity of Z

••
•• ••
••

••
••
O O
•• •• •• ••
••

••
H O Cl O H O Br O
•• •• • • •• •• • •

Cl is more electronegative than Br

HClO3 > HBrO3

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 Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different

numbers of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

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 Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water

A Brønsted acid is a proton donor

A Lewis acid is a substance that can accept a pair of electrons

A Lewis base is a substance that can donate a pair of electrons

•• ••
H+ + OH-

••
H O H
•• ••
acid base
H H
H+ +
••

N H H N H
H H
acid base 13
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 Lewis Acids and Bases

F H F H Adduct: a
product of the
F B + F B

••
N H N H reaction of a
Lewis acid and
F H F H a base to form
a new
acid base combination
(electrophile) (nucleophile)

No protons donated or accepted!

Let’s look at this reaction, and others like it more closely.

To see what’s really going on we need to look at the MOs.

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Diatomic Molecular Orbital
Theory
• In the case of diatomic molecules, the interactions are easy to see and may be
thought of as arising from the constructive interference of the electron waves
(orbitals) on two different atoms, producing a bonding molecular orbital, and the
destructive interference of the electron waves, producing an antibonding
molecular orbital
•This Approach is called LCAO-MO
(Linear Combination of Atomic Orbitals to Produce
Molecular Orbitals)

A Little Math is need to understand

Only a Little I promise!

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 How to impress your friends and family!
Making Molecular Orbitals
Antibonding

Bonding

In this case, the energies of the A.O.’s are identical 23

 Molecular Orbital of H2
The lowest energy state of two isolated hydrogen atoms is two 1s orbitals
each with one electron. As the nuclei approach each other, the lowest
energy state becomes a molecular orbital containing two paired electrons.

This lobe represents the orbital or wavefunction of the electrons delocalized

around the two protons. This is a bond.
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Energy levels of bonding and antibonding molecular
orbitals in hydrogen (H2).

A bonding molecular orbital has lower energy and greater stability than
the atomic orbitals from which it was formed.

An antibonding molecular orbital has higher energy and lower stability

than the atomic orbitals from which it was formed.

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 26
10.6
An analogy between light waves and atomic
wave functions

Amplitudes of wave
functions are added

Amplitudes of wave
functions are subtracted

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 Quantum States in H2 (as computed)
H2 also has other electronic quantum states with corresponding allowed
energies. These molecular orbitals have lobe structures and nodes just
like atomic orbitals.
0.735 Å
R= (H2)
R=
This diagram shows (H) (H)
some allowed energy
levels for atomic H 2s 2s
and molecular H2.

(R =  denotes the two

atoms at “infinite
separation” - no bond.)

The orbitals are filled

with electrons starting
with the lowest energy,
1s 1s
just like atoms.


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 Quantum States in H2 (as computed)
H2 also has other electronic quantum states with corresponding allowed
energies. These molecular orbitals have lobe structures and nodes just
like atomic orbitals.
R= 0.735 Å
(H) (H2)

2s

1s


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 Quantum States in H2: Allowed Energies
First let’s ignore the wavefunctions (orbitals), and consider only the
allowed energies, just as we did with atoms. What do we observe?

R= 0.735 Å
(H) (H2)

2s

1s


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 Quantum States in H2
The energy of the H2 molecule is lower than the energy of two isolated H
atoms. That is, the energy change of forming the bond is negative.

R= 0.735 Å We call this molecular orbital a bonding

(H) (H2)
orbital for this very reason.

The other orbitals have higher energies than

2s the atomic orbitals of H.

Electrons in these orbitals would not

contribute to the stability of the molecule.

H2 contains the simplest kind of bond, a pair

of electrons delocalized between two nuclei,
1s
symmetric to rotation about the interatomic axis.

s This is known as a sigma (s) bond.
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 Molecular Orbitals in H2
The next-lowest energy orbital is unoccupied. As it lies above the
highest atomic orbital, we refer to it as an anti-bonding orbital.

R= 0.735 Å Look also at the shape of the lobes:

(H) (H2) The anti-bonding orbital has a node between
the two nuclei.

2s Where the bonding orbital has an electron

density build-up between the nuclei, the anti-
bonding orbital would have a reduced
electron density (y 2).
This orbital is called the
s* Lowest Unoccupied Molecular
Orbital (LUMO)

1s
 This orbital is called the
Highest Occupied Molecular
s Orbital (HOMO) 32
 Molecular Orbital Theory
The solution to the Wave Equation for molecules leads to quantum
states with discrete energy levels and well-defined shapes of electron
waves (molecular orbitals), just like atoms.

Each orbital contains a maximum of two (spin-paired) electrons, just like atoms.

Bonds form because the energy of the electrons is lower in the molecules than it
is in isolated atoms. Stability is conferred by electron delocalization in the
molecule as they are bound by more than one nucleus (longer de Broglie
wavelength).

This gives us a convenient picture of a bond as a pair of shared (delocalized)

electrons. It also suggests some simple (and commonly-used) ways of
representing simple s bonds as:

1. A shared pair of electrons (dots)

H:H

2. A line between nuclei.

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H-H
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Reaction Mechanisms
How do the atoms of the reactant molecules
rearrange to form the product molecules?
What is the sequence of bond breaking and
bond making?

What are the energetics of the process?

How do the electrons flow?

What molecular orbitals are involved?

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 How do you analyze a mechanism?

Follow the Electrons. Push your arrows.

H F

+ H F N
N
H H H H
H H

What orbitals are involved?

What are the important MOs

of HF and NH3?
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Restating the Lewis Acid-Base Definition:

a) Base: has e- pair in HOMO of

correct energy and symmetry

b) Acid: has LUMO of correct energy

and symmetry

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