Protolytic reactions (Acid-base reactions)

The nature of a protolytic reaction is transferring of a proton (H+).

The substances reacting in protolytic reaction are called acids and bases.

There are three theories that identify a singular characteristic which defines an acid and a base:

The Arrhenius theory of acids and bases

It applies only to aqueous (water) solution.

Acids are substances which produce hydrogen ions in aqueous solution.

Bases are substances which produce hydroxide ions in aqueous solution.

The BrnstedLowry (BrnstedLowry) theory of acids and bases

This definition is based on the idea that in an acidbase reaction, a proton is transferred from an acid to a
base (a proton is a hydrogen ion, H+).

An acid is a proton (hydrogen ion) donor.

A base is a proton (hydrogen ion) acceptor.

Substances like water, which can act as either acids or bases, are described as amphoteric.

The Lewis theory of acids and bases

An acid is an electron pair acceptor.

A base is an electron pair donor.

Neutralisation

Neutralization is a reaction between an acid and a base that produces water and a salt. The general reaction
for the neutralization reaction is shown below.
We will work with the BrnstedLowry theory of acids and bases.

Hydrochloric acid is an acid because it donates a proton to water. This means that water is acting as a
BrnstedLowry base. The water is accepting a proton.

HCl + H2O H3O+ + Cl

acid base

An acid can only give off a proton (H +), if there is a base that can take it up. (The proton is incapable
of independent existence.)

When ammonia reacts with water, it accepts a proton from the water and becomes an NH 4 .

NH3 + H2O NH 4 + OH
base acid

If a reactant is linked to a product by the transfer of a proton we call this pair a conjugate pair.

An acid, and a base such that differ only in the presence or absence of a proton are called a conjugate
acid-base pair. Consider the following reaction:

HCl + H2O H3O+ + Cl

acid base acid base

Looking at the forward reaction: Looking at the reverse reaction:

Cl is the conjugate base of the acid HCl
HCl is the conjugate acid of the base Cl
H3O+ (oxonium) is the conjugate acid of the base H2O.
H2O is the conjugate base of the acid H 3O+.

BrnstedLowry acids:

neutral molecules: HCl, HNO3, H2SO4, H3PO4, H2O

ions: HSO 4 , H2P O 4 , HP O 4 , H3O+, NH 4

BrnstedLowry bases:

neutral molecules: H2O, NH3

ions: Cl, S2, OH, NO 2

Substances like water, which can act as either acids or bases, are called amphoteric (ampholytes).
Strong and weak acids and bases

It is important to understand the difference between dilute and weak, and concentrated and strong when you
are talking about acids and bases:
A strong acid or strong base is almost completely ionised (dissociated into ions) in water solution. The
acid or base molecule does not exist in aqueous solution, only ions.
A weak acid or weak base is only partially ionised in solution.
A concentrated acid or concentrated base has a large number of moles per unit volume of the acid or
base concerned.
A dilute solution has a small number of moles relative to the solvent.

Acids and bases are not all equal strength in giving off and taking up H+.
The strength of an acid its ability to donate protons; the strength of its base its ability to accept protons.

Strong acid is almost completely ionised in solution.

HCl (aq) + H2O (l) H3O+ (aq) + Cl (aq) [HCl] 0
In a 6 M (6 mol dm3) solution of hydrochloric acid, 99.996% of the HCl molecules react with water to form
H3O+ and Cl ions.

(A solution with a molar concentration of 1 mol/L (1 mol dm3) is equivalent to 1 molar (1 M).)

Vinegar is a weak acid because it is not very good at transferring of H + ions to water. In a 1 M solution, less
than 0.4% of the CH3COOH molecules react with water to form H3O+ and CH3COO ions.

acetic acid CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO (aq)

More than 99.6% of the acetic acid molecules remain intact.

When an acid HA dissolves in water, the following equilibrium is established:

HA (aq) + H2O (l) H3O+ (aq) + A (aq) HCl (aq) + H2O (l) H3O+ (aq) + Cl (aq)

The position of the equilibrium indicates the strength of the acid. For a strong acid, the equilibrium favours
the products, and the reaction goes almost to completion. For a weak acid, the equilibrium favours the
reactants with a relatively small amount of H3O+ (aq) produced.
[H 3O ] [A ]
Kc
[HA] [H 2 O]
In fact, the [H2O] is almost constant and it is included in the equilibrium constant Ka 1
[H 3O ] [A ]
K c [H 2 O]
[HA]

1
Pure solids or liquids are excluded from the equilibrium expression because their effective concentrations stay constant
throughout the reaction. The concentration of a pure liquid or solid equals its density divided by its molar mass. The density of a
pure liquid or solid is the same, regardless of how much pure liquid or solid is present.

Only the concentrations of gases (g) and substances in solution (aq) are included in the equilibrium expression.
so we use a new equilibrium constant, Ka, called the acid dissociation constant:
[H 3O ] [A ]
Ka K a K c [H 2 O]
[HA]

Analogous to the value of the equilibrium constant, as well as the value of the acid dissociation constant,
depends on the temperature.

The acid dissociation constant, Ka, is a measure of the strength of an acid. The higher its value, the stronger
the acid (i.e. the more readily it ionises in water).

Values of Ka are small, and it is usual to convert them to a logarithm (to base 10) of their value (pKa)
pK a log10 [K a ]

pKa converts Ka number to a logarithmic scale that makes it easier to compare strengths of different acids.

Ka > 102 strong acids (HClO4, HCl, HI, HNO3).

104< Ka < 102 moderately strong acids (H3PO4, HCOOH).
4
Ka < 10 weak acids (H2CO3, H2S).
Analogous to the acid dissociation constant, Ka, there is the base dissociation constant, Kb, describing a
measure of the strength of a base. The higher its value, the stronger the base (i.e. the more readily it ionises
in water).
B (aq) + H2O (l) BH+ (aq) + OH (aq) NH3 (aq) + H2O (l) NH 4 (aq) + OH (aq)

[BH ] [OH ] [NH 4 ] [OH ]

Kb K b ( NH 3 )
[B] [NH 3]

The relative strength of conjugate acid-base pairs

Some acids are better proton donors than others; likewise, some bases are better proton acceptors than
others.

The stronger an acid is, the weaker its conjugate base will be. The weaker an acid is, the stronger its
conjugate base will be.

Strong acids have a weak conjugate base.

Example: HCl is a strong acid. If HCl is a strong acid, it must be a good proton donor. However, the Cl ion
is a poor proton acceptor. Thus, the Cl ion must be a weak base.

HCl (aq) + H2O (l) H3O+ (aq) + Cl (aq)

Strong bases have a weak conjugate acid.

Example: Lets consider the relationship between the strength of the ammonium ( NH 4 ) and its conjugate
base, ammonia (NH3). The NH 4 ion is a weak acid because ammonia is a reasonably good base.
 NH3 (aq) + H2O (l) NH 4 (aq) + OH (aq)

The more readily a substance gives up a proton, the less readily its conjugate base accepts a proton.
Similarly, the more readily a base accepts a proton, the less readily its conjugate acid gives up a proton. In
other words, the stronger an acid, the weaker is its conjugate base; the stronger a base, the weaker is its
conjugate acid.
The words acid and base are
functional terms and not labels.
They describe what a substance
does, rather than what it is.
R. von Handler

Autoprotolysis of water
In autoprotolysis a proton is transferred between two identical molecules, one of which acts as a Brnsted
Lowry acid, releasing a proton which is accepted by the other molecule acting as a BrnstedLowry base.
As it was discussed previously on BrnstedLowry acids and bases, water is also amphoteric, capable of
acting as either a BrnstedLowry acid or base.
Water undergoes autoprotolysis in the self-ionisation (self-ionization, autoionization, autodissociation) of
water reaction.

H2O (l) + H2O (l) H3O+ (aq) + OH (aq) (endothermic reaction)

[H 3O ] [OH ]
The equilibrium constant expression for the dissociation of water is Kc
[H 2 O] [H 2 O]

K c [H 2 O]2 [H 3O ] [OH ]

Since dissociation takes place to a very small extent (the degree of ionisation of water is very low (nearly
one molecule ionises out of 550 molecules)), the concentration of undissociated water molecules, [H2O],
may be regarded as constant. The concentration of liquid water, [H2O], is essentially constant at any given
temperature.
The constant [H2O] can be combined with Kc, producing a new equilibrium constant Kw, K with the subscript
w for water. (The concentration of water is incorporated into Kw.)
K w [H 3O ] [OH ]

Kw the ion-product constant for water, the ion product constant of/for water, the ionic product of/for water
(the dissociation constant for water the ionisation constant (ionization constant) for water,
the water ionization constant, the water ion product, the constant ionic product for water)
The value of Kw is very small, in accordance with a reaction that favors the reactants. At 25C, the
experimentally determined value of Kw in pure water is 1.0 1014 K w [H 3O ] [OH ] 10 14 .
Kw, like all equilibrium constants, is temperature dependent.

Question 1: Calculate the oxonium ion (H3O+) and hydroxide ion (OH) concentration of water at 25C, Kw = 1014.
Solution:
1. Write the equation for the ionic product of water:

2. Substitute in the value for Kw:

3. Since [H3O+] = [OH]

4. Take the square root of both sides of the equation to find [H3O+]:

5. Since [H3O+] = [OH]

For any given temperature, [H3O+] = [OH] for water, so water is neutral at all temperatures.
Since the reaction is endothermic, as temperature increases, production of products are favoured (the value
of Kw increases, but [H3O+] = [OH]. As the temperature increases, the water remains neutral.

Pure water is a very weak electrolyte (it is regarded as a non-conductor), yet even the purest water has a
small conductivity as it ionises to a very slight extent.
Electrolytes are substances (fluids) that conduct electricity. Pure water does not conduct electricity. Water
molecules do not dissociate significantly to form charge carriers (ions).

In water solutions [H3O+] and [OH] are inversly proportional to each other: [H3O+] [OH].
If [H3O+] is increased by adding an acid to water, there must be the directly proportional decrease of [OH ],
and vice versa, if [OH] is increased by adding a base to water, there must be the directly proportional
decrease of [H3O+] ( [OH] [H3O+]).
Question 2: Calculate [OH], if HCl (aq) was added to to pure water at 25 C and a solution with
[H3O+] = 1010 was obtained.

The pH scale: Acidic, neutral and basic solutions

The pH scale is a way of gauging (measuring) the acidity or alkalinity (basicity) of a solution. It is calculated
using: pH = log10[H+] ( pH = log10[H3O+] )
Adding an acid to water increases the H + (H3O+) concentration, and decreases the OH concentration. An
alkali (base) does the opposite.
H3O+ is commonly called hydronium ion. It is also called hydroxonium ion or oxonium ion. Hydronium ion
is formed by combination H+ and H2O molecule H+ (aq) + H2O (l) H3O+ (aq)
In acid-base equilibria, H+ (aq) and H3O+ (aq) are used interchangeably. The are interchangeable ways to
describe the presence of protons in solution.

Since, large powers of ten (107, 1014) are clumsy to deal with, for convenience the Danish chemist
Srensen (Srensen) at the Carlsberg Laboratory defined pH as the negative logarithm (to the base 10) of
hydrogen ion concentration.
pH = log10[H+]
Acidity or basicity of solutions is expressed by the hydrogen ion exponent and the symbol pH for the
numerical value of this potenz (power). The exact meaning of the p in pH is disputed; pH may stand
stands for power of hydrogen or the p stands for the German Potenz (meaning power). Others refer to
French puissance (also meaning power, based on the fact that the Carlsberg Laboratory was
French-speaking). Another suggestion is that the p stands for the Latin terms pondus hydrogenii (quantity
of hydrogen), potentia hydrogenii (capacity of hydrogen), or potential hydrogen.

The negative sign in front of the log tells us that there is an inverse relationship between pH and [H+]: when
pH increases, [H+] decreases, and vice versa.

The lower the pH value, the more acidic the solution and the higher the concentration of H+. The higher the
pH value, the more basic the solution and the lower the concentration of H+.
Given the pH of a solution, we can also find [H+]
[H+] = 10pH

Both acid strength and concentration determine [H+] and pH.

The [OH] for an aqueous solution is defined in the same way for [OH]
pOH = log10[OH] and [OH] = 10pOH
For aqueous solutions at 25C:
For a neutral solution, pH = 7 [H3O+] = [OH]
Acidic solutions have pH < 7 [H3O+] > [OH]
Basic solutions have pH > 7 [H3O+] < [OH]

Solutions
neutral

acidic basic

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0 1 2 3 4 5 6 7 8 9 10 11 12 13
[H3O ]+
10 10 10 10 10 10 10 10 10 10 10 10 10 10 1014
pOH 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
14 13 12 11 10 9 8 7 6 5 4 3 2 1

[OH ] 10 10 10 10 10 10 10 10 10 10 10 10 10 10 100

For any aqueous solution at 25C: pH + pOH = 14

Question 3: What is the pH value of the obtained solution (Question 2)? Is it neutral, acidic, or basic?

Question 4: A household ammonia solution has a pH of 11.92. What is the pOH and the concentration of
OH in it?

Measuring pH
pH can be measured in several ways. Usually it is measured with a coloured acid-base indicator or a pH
meter.
An acid-base indicator (pH indicator) is either a weak acid or weak base that exhibits a color change as the
concentration of hydrogen (H+) / oxonium (H3O+) or hydroxide (OH) ions changes in an aqueous solution.
Indicators are substances that change color depending on the pH of the solution. Because they have such
vivid color changes, only small amounts of indicators must be added to a solution which also limits any side
effects they might have on the observed reacion.
Phenolphtalein, methyl orange, litmus are all indicators that are commonly used in the laboratory.
A particular type of acid-base indicator is a universal indicator, which is a mixture of multiple indicators that
gradually changes color over a wide pH range. The indicators are chosen so mixing a few drops with a
solution will produce a color that can be associated with an approximate pH value.
Many plants or plant parts contain anthocyanins. Anthocyanins can be extracted with water or other solvent.
They are red in acidic solutions and blue in basic. Red cabbage, rose petals, blueberries, blackcurrent can
also be used as an acid-base indicator.
Coloured indicators are a crude measure of pH, but are useful in certain applications, pH meters are more
accurate, but they must be calibrated prior to use. Calibration means setting to a standard. A pH meter is
calibrated with a solution of known pH often called a buffer.

Hydrolysis of salts (Salt hydrolysis)

When an acid reacts with a base the process is called neutralization and gives water and salt as products. The
reaction of a salt with water, the reverse of neutralization, is called salt hydrolysis. The reactions of ions
with water are frequently called hydrolysis reaction. (hydrolysis splitting by water). It is the reaction of the
cation or the anion or both the ions of the salt with water to produce either acidic or basic solution (to
produce acidity or alkalinity).
Depending on the nature of an acid or a base there can be four types of salts:
I. salt of a weak acid and a strong base,
II. salt of a strong acid and a weak base,
III. salt of a weak acid and a weak base
and
IV. salt of a strong acid and a strong base.