Reversible reactions

A reversible reaction is one where there is a forward and backward reaction occurring:

The double arrow signifies a reversible reaction.

If in the above reaction the concentrations of A, B, C, D do not change, although the reaction
is still in progress, then the forward rate must equal the backward rate. A situation known as
dynamic equilibrium has been reached.
Equilibrium constants
Any dynamic equilibrium can be described in terms of its equilibrium constant, Kc.
The equilibrium constant is the product of the molar concentrations of the products raised to
the power of its coefficient in the stoichiometric equation, divided by the product of molar
concentrations of the reactants, each raised to the power of its coefficient in the
stoichiometric equation.
So for the reaction:

The equilibrium constant is given by:

Where [] represents the concentration of the species in moldm-3.

For gaseous systems, we use Kp instead of Kc. Here, the species are shownin the equilibrium
equation in terms of their partial pressures. (In a mixture of gases, the proportion of the total
pressure due to a particular gas is dependant on its mole fraction).
Introduction
Le Chateliers principle states:
The position of the equilibrium of a system changes to minimise the effect of any
imposed change in conditions.
This principle applies to any reaction that is in equilibrium.

The effect of concentration changes on equilibrium

Changing concentration of a reactant or product does not change the numerical value of the
equilibrium constant, but it does change the position of the equilibrium.
In general, the position of the equilibrium is shifted towards the right if the concentration of
a reactant is increased or to the left if the concentration of a product is increased.
At the start, when the change is made, the mixture is not at equilibrium, but equilibrium is
eventually restored.
The effect of pressure changes on equilibrium
For a reaction involving gases, altering the pressure may cause a change in the position of the
equilibrium.
For a reaction where there is an increase in the number of moles from reactants to products,
increasing the pressure moves the equilibrium to the left.
Where there is a decrease in the number of moles from reactants to products, increasing the
pressure moves the equilibrium to the right. The equilibrium constant remains the same.
The effect of temperature changes on equilibrium
The change that takes place when temperature is changed depends upon whether the forward
reaction is exothermic or endothermic.
If the forward reaction is exothermic then the backward one is endothermic.
If the temperature is increased, the equilibrium moves to the left, since an endothermic
reaction will tend to reduce the temperature.
Conversely, if the temperature is decreased then the equilibrium, moves to the right.
The effects of catalysts on equilibrium
A catalyst has no effect on the position of the equilibrium. However, it does increase the rate
of both the forward and backward reactions, decreasing the time taken to reach equilibrium.

Acids and bases

In 1923 Bronsted and Lowry proposed the proton transfer theory of acids and bases.
Their theory states that an acid is a substance which donates protons, and a base is a
substance which accepts protons.
If we observe the behaviour of a strong acid such as hydrochloric acid, we note that the
hydrogen chloride fully dissociates, forming hydrogen ion, H+, and chloride ions, Cl.
The hydrogen ions are also known as protons since a hydrogen ion consists of a single proton
only. These protons are donated to the water molecules forming oxonium ions, H3O+.

If we now observe a weak acid such as ethanoic acid, the acid molecules are only
partially dissociated in water, and so the equilibrium is established:

Even so, the acid molecules donate protons to water molecules.

Strong bases such as an alkali metal hydroxides are fully ionised in water:

They are bases because the hydroxide ions can accept hydrogen ions:

This reaction is common to all neutralisation reactions between acids and bases in aqueous
solution.
Note: In aqueous solutions the hydrogen ions exist in their hydrated forms, that is, as
oxonium ions.
If we examine an example of equilibria a little more closely, we can begin to label the species
in the equilibrium mixture.
For example:

The equilibrium mixture is said to consist of two conjugate pairs of acids and bases:
NH3 and NH4+ are a conjugate pair. HCl and Cl- are a conjugate pair also.
Note: In each conjugate pair, the acid and base only differ from one another by a proton.
Each acid has its own conjugate base.
A strong acid always has a weak conjugate base.
A weak acid always has a strong conjugate base.
Dissociation constants
The equilibrium law can be applied to aqueous solutions of acids. For example, the following
equilibrium is established in an aqueous solution of ethanoic acid:

The equilibrium constant is given by Ka =

[] represents concentration.
Ka is called the Acid Dissociation Constant.
The acid dissociation constant is a measure of the strength of an acid. For an acid such as
hydrochloric acid which is virtually fully dissociated in aqueous solution, its value is
extremely large.
On the other hand, for weak acids, values of Ka can be extremely small. It is often more
convenient to compare the strengths of acids using pKa values, where pKa is given by pKa =
-lgKa.

For most acids this gives the range of values from 0-14.
Strong acids have low pKa values and weak acids have large values.
The Ionic product of water
The electronic conductivity of even the purest water never falls to exactly zero. This is due to
the SELF-IONISATION of water. This can be represented by:

Applying the equiibrium law to this equilibrium, we obtain:

Kw = [H3O+][OH-] eq

Kw = [H+][OH-] eq

Kw is called the ionic product of water. It has units of (concentration)2; that is mol2dm-2. The
exact value depends on the temperature.At 25oC its value is 1.0 x 10-14.
This gives a pKw value of 14, where: pKw = -lgKw
The ionic product of water is related to the dissociation constants pKa and pKb of an acid and
its conjugate base respectively.
pKa + pKb = pKw = 14 (at 25o C)
Thus, if the pKa value of an acid is known, the pKb value of its conjugate base can be found.
How to calculate pH
The concentration of oxonium ions in solution can be expressed in terms of the pH scale.
The pH of a solution is the logarithm to base 10 of the reciprocal of the numerical value
of the oxonium ion concentration:
pH = lg 1/H30+
= -lg [H30+]
= -lg [H+]
The pH of a neutral solution can be calculated directly from the ionic product of water.
Kw = [H3O+] = [OH-] OR [H+] = [OH-]

[H+] = 10-7
pH = 7 for neutral solutions.
Acidic solutions have a pH less than 7 at 25oC.
pH values of bases
The concentration of hydroxide ions in a solution can be expressed in terms of pOH. This is
given by: pOH = -lg[OH-]
It is possible to write an expression relating pH and pOH as pKw = pH + pOH
At 25oC: pH + pOH = 14
Calculation examples
Calculate the pH value of 0.001 moldm-3 solution of NaOH at 25oC.
[OH-] = 10-3
Therefore: p[OH-] = 3
If pH + 3 = 14, then pH = 11
Calculate the pH of a solution of 0.1M hydrochloric acid at 25oC:
[H+] = 10-1 moldm-3
pH = -log10-1 = 1
Types of buffers
A buffer solution is a solution the pH of which does not change significantly when a small
amount of acid or base is added to it. There are four categories of buffers.
Strong acid buffers
A strong acid such as nitric acid can act as a buffer with a low pH. Strong acids are fully
dissociated in aqueous solution and thus the concentration of oxonium ions is high.
The addition of a small amount of acid or base to the acid will thus havea negligible effect on
the pH of the acid.
To calculate the pH use: pH = -log[H+]

Strong base buffers

A strong base can be used as a buffer with high pH. The addition of small amount of acid or
base has negligible effect on the pH. This can be checked using the equation: pH + pOH = 14
Weak acid buffers
Buffer solutions with constant pH values of between 4 and 7 can be prepared from a weak
acid and one of its salts. Ethanoic acid and sodium ethanoate are often used for this purpose.
Sodium ethanoate in water is fully ionised:

On the other hand, ethanoic acid is only partially ionised:

If acid is added this equilibrium shifts to the left. The additional H3O+ ions are thus removed
and the pH remains constant.
The presence of the sodium ethanoate in the buffer solution ensures that there is a large
reservoir of CH3COO- ions to cope with this addition of acid.
If the base (OH-) is added, then the following happens:

Removal of H3O+ ions by this reaction results in the equilibrium shifting to the right. The
concentration of H3O+ ions and thus the pH of the solution remains constant.
The presence of the ethanoic acid ensures that there is a large reservoir of undissociated
CH3COOH molecules ready to dissociate in order to cope with the addition of base.
Weak base buffers
Buffer solutions with constant pH values between 7 and 10 can be prepared from a weak base
and one of its salts. A solution of ammonia and ammonium chloride is typically used.
In aqueous solution the ammonium chloride is fully dissociated:

The ammonia is only partially dissociated:

If acid is added it is neutralised by the OH- ions. Equilibrium shifts to the right, thus
maintaining the concentration of OH- ions and thus a constant pH.
If base is added the equilibrium shifts to the left, thus maintaining the concentration of the
OH- ions constant.
The presence of ammonium chloride in the buffer solution ensures that there is a large
reservoir of NH4+ ions to cope with the addition of base.
Calculating

Therefore:

Ionic compounds tend to dissolve in polar solvents such as water.

The solubility is due to the solvation (or in the case of water, hydration), of ions by the polar
water molecules.
A solution is saturated when no more solute will dissolve in it.

If the solute is an ionic compound, then these ions in the saturated solution are in dynamic
equilibrium with the excess solid. In the case of silver chloride for example, the following
equilibrium is set up:

By applying the equilibrium law:

Ksp = [Ag+][Cl-]eq
Ksp is called the solubility product of silver chloride.
The AgCl(s) term is constant and is incorporated in to Ksp.
The solubility of silver chloride can be expressed in terms of the concentration (c) of
dissolved AgCl in water.
This concentration equals the concentrations of both ions in solution:
[Ag+] = [Cl-] = c
So, the solubility of silver chloride can be related to its solubility product by:

The units of Ksp in the case of AgCl are (concentration)2 or mol2dm-6.

The common ion effect
Let us now consider the equilibrium established when silver chloride dissolves in water to
form a saturated solution:

If we now add more chloride ions (by adding sodium chloride solution for example) the
equilibrium shifts to the left.
This effect is known as the common ion effect. In this case, chloride is the common ion. It is
common to both silver chloride and the sodium chloride.

Since the addition of the common ion results in shifting the equilibrium to the left, silver
chloride is precipitated. The addition of the common ion has reduced its solubility. The
same effect is produced if silver nitrate solution is added. In this case the common ion is
silver.
It follows that the solubility of an electrolyte in an aqueous solution containing a common ion
is less than the solubility in water.