Acids

&
Bases
How can we distinguish
acids and bases?
 Early Theories
French chemist Lavoisier proposed in 1777
that oxygen was the ‘universal acidifying
principle’.

He believed that an acid could be defined as

a compound of oxygen and a non-metal.
ex: HNO3 (nitric acid) H2 SO 4 (sulfuric acid)

Does every acid contain oxygen?

 Early Theories
Eventually, it was realised that the element common to
all acids was, hydrogen, and this led to the first
modern definition of an acid put forward by Arrhenius.

He defined acids as substances which increase the

concentration of hydrogen ions (H+), or more
accurately, hydronium ions (H3O+), when dissolved in
water.
 Early Theories
Arrhenius suggested that an acid could be defined as a substance that
dissociates in water to form hydrogen ions (H+) and anions, while a
base dissociates into hydroxide (OH−) ions and cations.

He also recognized that the hydrogen and hydroxide ions could form
water, and the cations and anions form a salt.

Arrhenius was very close to the theory that is widely used to explain
acid and base properties today, but his focus was only on aqueous
systems.

HCl(aq) + NaOH(aq) NaCl(aq) + H2O (l)

 A broader theory was needed to account for
reactions occurring without water, and especially for
the fact that some insoluble substances show base
properties.

water and soluble salts are formed when an

insoluble base reacts with dilute acid

Additionally, the Arrhenius theory

could not explain the reaction
between gases.
 Brønsted - Lowry Theory
In 1923 two chemists, Martin Lowry and Johannes Brønsted
working independently, published similar conclusions
regarding the definitions of acids and bases.
Their findings overcame the limitations of Arrhenius’ work
and have become established as the Brønsted–Lowry
theory.

This theory focuses on the transfer of H+ ions during an acid–base

reaction:
acids donate H+
bases accept H+
 Brønsted - Lowry Theory
For example, in the reaction between HCl and NH 3 :

HCl transfers H+ to NH3 and so acts as an acid,

NH3 accepts the H+ and so acts as a base.
 Brønsted - Lowry Theory
Hydrogen atoms contain just one proton and one electron, so when
they ionize by losing the electron, all that is left is the proton.
Therefore H+ is equivalent to a proton, and we will use the two
terms interchangeably here.

The Brønsted–Lowry theory can therefore be stated as:

a Brønsted–Lowry acid is a proton (H+) donor;
a Brønsted–Lowry base is a proton (H+) acceptor.
A proton refers to a hydrogen ion (H+) which exists as the
hydronium ion (H 3 O+) in aqueous solution.

All Brønsted–Lowry acids contain hydrogen, as, by definition,

they must be able to donate a hydrogen ion to another
species.
All Brønsted–Lowry bases must have a lone pair of electrons
to form a bond with the hydrogen ion donated to them by the
Brønsted–Lowry acid.
Is water a Brønsted - Lowry acid
or a Brønsted - Lowry base?
Species that are able to act as either a Brønsted–Lowry acid or a
Brønsted–Lowry base are known as being amphiprotic.
For example, water is able to act as a Brønsted–Lowry acid or a
Brønsted–Lowry base, as shown below:
 Conjugate acid-base pairs
In Brønsted–Lowry theory, an acid can only behave as a proton
donor if there is also a base present to accept the proton.

In forward reaction; In backward reaction;

HA acts as an acid, donating a BH+ is acting as an acid, donating
proton to B while B acts as a its proton to A− while A− acts as a
base, accepting the proton from base accepting the proton from
HA. BH+.
 Conjugate acid-base pairs
In other words acid HA has reacted to form the base A−,
while base B has reacted to form acid BH+.
The acid–base pairs related to each other in this way are called
conjugate acid−base pairs, and you can see that they differ by
just one proton.
The conjugate acids of the given bases are deduced by adding H+ to each
species. Remember to adjust the charge by +1 in each case.
The conjugate bases of the given acids are deduced by removing H+ from
each species. Remember to subtract 1+ from the net charge in each case.
 acid base acid base

base acid base acid

acid base acid base

To be amphiprotic the substance must be able to both accept and release
protons:

acid behaviour as protons are released

base behaviour as protons are accepted

Properties of Acids and Bases
Classification leading to generalizations is an important
aspect of studies in science.
For example, acids were classified together because they
were shown to have similar chemical properties.
Over time it was recognized that many substances share
these acidic properties, and so the classification
broadened.
Similarly, grouping of compounds as bases and alkalis
occurred on the basis of ‘experimental evidence’ for
their properties.
 Bases
+
Where an acid produces an H ion, a base either produces an
-
OH ion (Arrhenius base or alkalis) or accepts H+ ion (Bronsted
- Lowry base).

The soluble bases are known as alkalis. When

-
dissolved in water they all release the OH ion
(hydroxide ion).
 Examples of Bases
metal oxides (most of them are insoluble in water)
Na2O, K2 O (soluble)
MgO, Cu2 O (insoluble)
metal hydroxides (most of them are soluble in water)
NaOH, Ba(OH)2 (soluble)
Ca(OH)2 (slightly soluble), Mg(OH)2 (insoluble)
ammonia (NH3 )
soluble carbonates
Na2CO3 , K2CO3
soluble hydrogencarbonates
NaHCO3 , KHCO3
 Bases can be classified as monoprotic, diprotic, and triprotic
according to their exchangeable hydroxide groups.

Monoprotic bases can either accept a single proton (Bronsted

-
base) or donate a single OH ion (Arrhenius base).
ex: NH3 , NaOH, amines (CH3 NH2 )
Diprotic Arrhenius bases have two exchangeable OH groups.
ex: Ca(OH)2
Triprotic Arrhenius bases have three exchangeable OH groups.
ex: Al(OH)3
 Acids
Each acid must contain at least one exchangeable hydrogen
atom.
Exchangeable hydrogen atoms usually form bonds with highly
electronegative atoms, such as oxygen, halogens or sulfur.
Depending on the number of exchangeable hydrogen atom,
acids are classified as;
monoprotic (ex: HCl)
diprotic (ex: H2 SO4 )
triprotic (ex: H 3PO4 )

The characterisation of an acid depends on empirical evidence such

as the production of gases in reactions with metals, the colour
changes of indicators or the release of heat in reactions with metal
oxides and hydroxides.
 Reactions of acids
Acids react with metals, bases, and carbonates to form salts.

The term salt refers to the ionic compound formed when the
hydrogen of an acid is replaced by a metal or another
positive ion.

There are three main types of reaction by which acids react to form salts:
1. Acid + metal→ salt + hydrogen
2. Acid + base → salt + water
3. Acid + metal carbonate/metal hydrogencarbonate → salt + water +
carbon dioxide
 Acid + metal → salt + hydrogen

More reactive metals such as sodium and potassium in

would react much too violently, while copper and other
less reactive metals such as silver and gold will usually
not react at all. This is partly why these less reactive Zinc reacted with HCl
metals are so valuable – they are much more resistant
to corrosion.
 Test for Hydrogen
Hydrogen gas can be tested
for by igniting a small
volume of the gas in an
inverted boiling tube.
The flammable gas burns
with a distinctive sound,
known as a 'squeaky pop'.

Nitric acid, HNO3 , does react with metals,

but it usually does not release hydrogen.
Acid + base → salt + water

The reaction between acids and bases to form a salt and water is
known as neutralization.
The reaction between an acid and a base is exothermic, meaning
that heat is released and the enthalpy change (ΔH) is negative.
The salt produced in neutralization reactions is composed
of a cation from the base and an anion from the acid.
Do neutralization reactions
always result in a neutral
solution?
 Acid + base → salt + water
Ba(OH)2 (aq) + 2HCl(aq) → BaCl (aq) + 2H O(l)
2 2

There is a need for equimolar quantities (stoichiometric

amounts) to get neutral solution.
For example, mixing equal volumes of barium hydroxide and
hydrochloric acid (of the same concentration) will result in an
alkaline solution since the base (hydroxide ions) is present in
excess.
Acid + carbonate salt + water +→
carbon dioxide
metal carbonate

metal
hydrogencarbonate
Baking soda (NaHCO3) and vinegar
(CH3COOH) react together and
release carbon dioxide gas

The reactions, like the reaction of acids with metals, involve

a gas being given off so they visibly produce bubbles, known
as effervescence.
Test for carbon dioxide:
The presence of carbon dioxide gas can be
tested by passing carbon dioxide through
limewater (calcium hydroxide).

If carbon dioxide gas is present, the

limewater turns a 'milky' colour as a solid
precipitate of calcium carbonate is formed.

Ca(OH)2 (aq) + CO2 (g) → CaCO (s) + H O(l)

3 2
 Acid- Base Indicators
Indicators act as chemical detectors, giving information about
a change in the environment.
The most widely used in chemistry are acid–base indicators that
change the color reversibly according to the concentration of
H+ ions in the solution.
The color change means that they can be used to identify the
pH of a substance.
Indicators are generally used either as aqueous solutions or
absorbed onto ‘test paper’.
Probably the best known acid–base indicator is litmus which is a
dye derived from lichens, and which turns pink in the presence of
acid and blue in the presence of alkalis.
It is widely used to test for acids or alkalis, but is not so useful in
distinguishing between different strengths of acid or alkali.
Universal indicator
Universal indicator is actually a mixture of indicators that
produces different colors in solutions of different pH.
The mixture is designed so that the colors produced as the pH
increases usually correspond to a ‘rainbow’ sequence.
The pH of aqueous solutions can be measured by using
universal indicator as either a solution or in paper form.
 pH meter
A pH meter produces a more accurate method of measuring pH, provided
they are correctly calibrated.
The electrode of the pH meter is placed in the solution to be tested and a
voltage is generated that is converted into a pH meter reading displayed
on the screen.
The pH meter is calibrated using
buffers of known pH, usually of pH
4.0, 7.0 and 10.0.
 Acid - Base Titrations
Neutralization reactions are used to calculate the exact
concentration of an acid or an alkali when the other concentration
is known. (the solution of known concentration is known as the
standard solution)
An acid–base indicator is used to determine the point where the acid
neutralises the base or vice versa.
Indicators are chosen due to their easily identifiable color changes.
 Acid - Base Titrations
titrant
1. The burette is filled with an acid of
known concentration (the titrant).
2. The titrant is added gradually to
the alkali of unknown
concentration (the analyte) until
the end-point/equivalence point is
reached where they exactly
analyte
neutralize each other.

titration apparatus
Acid - Base Titrations

phenolphthalein
 pH Scale
The pH scale is used to determine how acidic or basic an aqueous
solution is.
The pH of a substance is a measure of the concentration of
hydrogen ions, [H+], in solution. It is defined as follows:

power concentration of
hydrogen ions, [H+]
 pH Scale
The pH number is inversely related to the [H+].
Solutions with a higher [H+] have a lower pH and vice versa.
Stronger and more concentrated acids have a lower pH, weaker and
more dilute acids have a higher pH.
In terms of hydroxide ions, a higher concentration of OH− ions, [OH−],
corresponds to a higher pH value and a lower [OH−] corresponds to a
lower pH value.
 pH Scale
pH numbers are usually positive and have no
units
Although the pH scale is theoretically an infinite
scale (and can even extend into negative numbers),
most acids and bases encountered will have positive
pH values.

A change of one pH unit represents a 10- fold

change in [H+].
This means increasing the pH by one unit represents
a decrease in [H+] by 10 times; decreasing by one pH
unit represents an increase in [H+] by 10 times.
 pH Calculations
From the definition of pH we can:
calculate the value of pH from a known concentration of H+;
calculate the concentration of H+ from a given pH.
For strong acids or bases, the [H+] or [OH−] in solution is equal to the
initial concentration of the strong acid or base. This is because
strong acids and bases completely dissociate in solution.

-3
Calculate the pH of 0.020 mol dm nitric acid, HNO3 (aq).
HNO3 (aq) →
+
H + NO3-

+ - -3
[H ] = [NO3 ] = [HNO3 ] = 0.020 mol dm
 pOH Calculations
The pOH of a solution can be calculated by taking the
negative log of the hydroxide ion concentration, [OH−], using
the following equation:
 The ionization of water
Pure water is a very poor conductor of electricity, which
means that it must have a low concentration of mobile
ions responsible for the electrical conductivity of
solutions.
Water molecules do dissociate however, but only to a very
small extent; this is known as the auto-ionisation of
water.
 The ionization of water

The concentration of water can be considered to be constant due to

the fact that so little of it ionizes, and it can therefore be combined
with Kc to produce a modified equilibrium constant known as Kw.

ionic product
constant of water
 The ionization of water

room temp.
Like any equilibrium expression, Kw is temperature-dependent, therefore,
at a certain temperature the product of [H+ ] and [OH- ] is a constant.
This means that as [H+ ] of a solution increases, [OH- ] decreases (and
vice versa).

-
for neutral solutions: [H+ ] [OH ]
-
for acidic solutions: [H+ ] [OH ]

for basic solutions: [H+ ] [OH- ]

 o
We will assume that all solutions have a same temperature of 25 C,
so the Kw value remains constant.
Therefore, using the value of the ionic product of water, Kw, the [H+]
and [OH−] of a solution can be calculated.
An aqueous solution has a pH of 3.20 at 298 K.
Determine the [H+] and [OH–] of the solution.
An aqueous solution has a pH of 3.20 at 298 K.
Determine the [H+] and [OH–] of the solution.