CHAPTER 20: Lattice Energy

20.1 Introduction to Lattice Energy

20.2 Born-Haber Cycles

20.3 Ion Polarisation

20.4 Enthalpy Changes in Solutions

Learning outcomes:

(a) explain and use the term lattice energy (∆H negative, i.e. gaseous ions to solid lattice).
(b) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the numerical
magnitude of a lattice energy.
(c) apply Hess’ Law to construct simple energy cycles, and carry out calculations involving such
cycles and relevant energy terms, with particular reference to:
(i) the formation of a simple ionic solid and of its aqueous solution.
(ii) Born-Haber cycles (including ionisation energy and electron affinity).
(d) interpret and explain qualitatively the trend in the thermal stability of the nitrates and
carbonates in terms of the charge density of the cation and the polarisability of the large
anion.
(e) interpret and explain qualitatively the variation in solubility of Group II sulfates in terms of
relative magnitudes of the enthalpy change of hydration and the corresponding lattice energy.
20.1 Introduction to Lattice Energy
What is lattice energy?

1) In a solid ionic crystal lattice, the ions are bonded by strong

ionic bonds between them. These forces are only completely
broken when the ions are in gaseous state.

2) Lattice energy(or lattice enthalpy) is the enthalpy change when one mole of solid
ionic lattice is formed from its scattered gaseous ions.

3) Lattice energy is always negative. This is because energy is always released

when bonds are formed.

4) Use sodium chloride, NaCl as an example. It can be described as the enthalpy

change when one mole of sodium chloride is formed from its scattered gaseous
sodium and chloride ions. The value is -787 kJ mol⁻¹.

5) Lattice energy is a good indication of the strength ionic bonds. The higher the
magnitude of lattice energy, the stronger the ionic bond formed. This is because
more energy is released when strong bonds are formed.

Factors affecting lattice energy

1) There are two factors which govern the magnitude of lattice energy:
i. Charge on the ions.
ii. Radius of the ions.

2) i. The higher the charge on the ion, the higher the lattice energy.
ii. This is because ions of higher charge have stronger attraction towards each
other. Hence more energy is released when bonds are formed between them.
 iii. For example, magnesium oxide, MgO has a higher lattice energy than sodium
chloride. This is because Mg²⁺ and O²⁻ have higher charge than Na⁺ and Cl⁻
ions.

3) i. The larger the ionic radius, the lower the lattice energy.
ii. This is because the attraction between ions gets weaker as the distance
between them increases. Hence less energy is released when bonds are formed
between them.
iii. For example, the lattice energy of sodium halides gets lower from sodium
fluoride to sodium iodide. This is because as the size of the halide ion
increases, the distance between sodium and halide ions increases.
Electron affinity

1) The first electron affinity, ΔHea1 is the energy released when one mole of electrons is
added to each atom in one mole of the atoms of the element to form one mole
of gaseous 1- ions.
For example:
Cl(g) + e⁻ → Cl⁻(g) ; ΔHea1 = -349 kJ mol⁻¹

2) The use of electron affinities are almost always confined to Group 6 and 7
elements.

3) Generally, first electron affinities are exothermic, this is because there is an

attraction between the positive nucleus and the incoming electron. Energy is
released when this attraction is set up.

4) Electron affinity is a measure of the attraction between the incoming

electron and the nucleus - the stronger the attraction, the more energy is
released.

5) The factors that govern the magnitude of electron affinity is the same as the
ones for ionisation energy - nuclear charge, distance between nucleus
and incoming electron and shielding effect of electrons.

6) Going down a Group, the magnitude of first electron affinity decreases. This
is because the distance between incoming electron and the nucleus increases,
therefore the attractive force between them is less. The increasing nuclear
charge is offset by the increasing shielding effect by inner electrons.

7) Take Group 7 as an example, the elements follow

the pattern described, except for fluorine. This is
because fluorine is a very small atom with high
electron density. A repulsion between electrons
is created hence the attraction between nucleus
and incoming electrons is less. In Group 6, oxygen
and the rest follow the exact same trend.

8) Group 6 elements have a lower electron affinity compared to their

corresponding Group 7 elements. This is because the nuclear charge of Group
6 elements is lower, less attraction is set up between the nucleus and outer
electrons, therefore less energy is released.
9) The second electron affinity, ΔHea2 is the energy released when one mole of
electrons is added to each gaseous 1- ions of to form one mole of gaseous 2-
ions.
For example:
O⁻(g) + e⁻ → O²⁻(g) ; ΔHea1 = +844 kJ mol⁻¹

10) Second electron affinities are usually endothermic, this is because energy is
required to add electrons into an already negative region due to the repulsion
between electrons.

Recall some enthalpy changes

1) Standard enthalpy change of formation, ΔH°f is the enthalpy change when one mole
of a compound is formed from its elements under standard condition.
The reactants and products must be in their standard states.
2Fe(s) + 1½O2(g) → Fe2O3(s) ; ΔH°f [ Fe2O3(s) ] = -824.5 kJ mol⁻¹

2) Standard enthalpy change of atomisation, ΔH°at is the enthalpy change when one mole
of gases atoms is formed from its element under standard conditions.
½H2(g) → H(g) ; ΔH°at [ ½H2 ] = +218 kJ mol⁻¹

20.2 Born-Haber Cycles

What are Born-Haber cycles?

1) Lattice energy cannot be determined experimentally, however, it can be

calculated using a special type of Hess' cycle, this is called the Born-Haber
cycle.

2) It assumes that the final product is the solid ionic compound. To make this
compound, we start with its elements in their standard states, and convert them
to ions in gaseous state. These ions are then converted to the solid lattice.
Lattice energy can be obtained by considering the energetics of the entire
process.
3) A typical Born-Haber cycle looks like this, take sodium chloride, NaCl as an
example:
Here, the final product is NaCl(s). To make
this, we begin with Na(s) + ½Cl2(g). This is
then converted step-by-step into Na⁺(g) +
Cl⁻(g). This is done using atomisation energy,
ionisation energy and electron affinity.

The energy released when the gaseous ions

join to form the lattice is the lattice energy.

By Hess' Law,
-411 = +107 + 496 + 122 - 349 + LE
LE = -411 - 107 - 496 - 122 + 349
LE = -787 kJ mol⁻¹

• -411 is the enthalpy change of formation.

• +107 is the enthalpy change of atomisation
of Na.
• +496 is the first ionisation energy of Na.
• +122 is the enthalpy change of atomisation
of ½Cl2.
• -349 is the first electron affinity of Cl.

Note:
1) Each level should only indicate one type of enthalpy change.
4) Another example, Born-Haber cycle of magnesium chloride, MgCl2.

The thing to note here is the

multiplication of atomisation
enthalpy and electron affinity
of Cl by 2 and also the use of
second ionisation energy for
Mg.

20.3 Ion Polarisation

Polarising power and polarisability

1) Not all ionic compounds are fully ionic, the same goes to covalent compounds.
Pure ionic and covalent bondings are extremes.

2) In an ionic compound, the positive charge on the

cation may attract the negative electron cloud of the
anion towards it. This results in distortion of the
electron cloud of the anion.

3) The factors which affect ion polarisation are:

i. the charge density of the cation.
ii. the size of the anion.

4) A cation is said to have a high charge density if it has a hogh charge spread
over a small volume. For example, Mg²⁺ has a higher charge density than Ba²⁺.
5) i. The higher the charge density of the cation, the higher the polarising power.
(Easier to polarise)
ii. The larger the size of the anion, the higher the polarisability. (Easier to be
polarised)

6) Ion polarisation causes ionic bonds to have a certain degree of covalent

character, making them impure.

Ion polarisation and thermal stability

Refer to Chapter 11: Group II, section 11.4.

20.4 Enthalpy Changes in Solutions

Recall enthalpy change of solution and hydration

1) Standard enthalpy change of solution, ΔH°sol is the enthalpy change when one mole
of ionic compounds is dissolved in water to form an infinitely dilute solution
under standard conditions.
MgCl2(s) + aq → MgCl2(aq) ; ΔH = ΔH°sol

2) Standard enthalpy change of solution can be exothermic or endothermic, that

is, some substance dissolve exothermically while others dissolve endothermically.
So, why is there a difference?

3) Standard enthalpy change of hydration, ΔH°hyd is the enthalpy change when one mole
of gases ions dissolves in water to form hydrated ions of infinite dilution under
standard conditions.
Ca²⁺(g) + aq → Ca²⁺(aq) ; ΔH = ΔH°hyd

4) Standard enthalpy change of hydration is

always exothermic, this is because when an
ion dissolves in water, bonds are formed between
the ions and water molecules. This bond is called
the ion-dipole bond.
5) Factors affecting the magnitude of hydration enthalpy are:
i. the size of the ion.
ii. the charge on the ion.

6) i. The larger the size of the ion, the lower the hydration enthalpy. For example,
hydration enthalpy of the Group II ions decreases down the Group.
ii. The higher the charge of the ion, the higher the hydration enthalpy. For
example, Group II ions have higher hydration enthalpy compared to their
corresponding Group I ions.

The process of dissolving

1) i. The process of dissolving is imagined as if the solid ionic lattice is first

broken down to form gaseous ions. Lattice energy is absorbed.
ii. These gaseous ions are then dissolved in water, this is how they exist in
the final solution. The energy involved here is hydration enthalpy.
iii. The energy involved in the entire process(from solid ionic lattice to hydrated
ions) is the solution enthalpy.

2) Therefore, take sodium chloride, NaCl as an example:

3) An example:

Solubility of Group II sulfates

1) The solubility of Group II sulfates decreases down the Group.

2) The solubility is governed by the sign of the enthalpy change of solution,

ΔH°sol. If ΔH°sol > 0, the sulfate is relatively insoluble. If ΔH°sol < 0, the sulfate is
relatively soluble.

3) The sign of ΔH°sol is governed by the relative magnitude of ΔH°hyd and ΔH°latt.

4) i. Going down the Group, if ΔH°hyd decreases faster than ΔH°latt, the
sulfates become more insoluble down the Group.
ii. Going down the Group, if ΔH°latt decreases faster than ΔH°hyd, the
sulfates become more soluble down the Group.

5) In the case of Group II sulfates, the former is true.

6) i. Hydration enthalpy decreases faster down the Group because the size of the
cations increases dramatically down the Group, the anion is a constant.
ii. Lattice energy decreases slower down the Group because the sulfate ion is
much larger than the Group II ions. As a result, the sulfate ion contributes to
a greater part in the magnitude of lattice energy. That is, the increase in size
of the cations is relatively insignificant.
CHAPTER 21: Electrode Potentials
21.1 Standard Electrode Potential
21.2 Measuring Standard Electrode Potential
21.3 Using E° Values
21.4 Cells and Batteries
21.5 Quantitative Electrolysis

(a) define the terms:

(i) standard electrode (redox) potential.
(ii) standard cell potential.
(b) describe the standard hydrogen electrode.
(c) describe methods used to measure the standard electrode potentials of:
(i) metals or non-metals in contact with their ions in aqueous solution.
(ii) ions of the same element in different oxidation states.
(d) calculate a standard cell potential by combining two standard electrode potentials.
(e) use standard cell potentials to:
(i) explain/deduce the direction of electron flow from a simple cell.
(ii) predict the feasibility of a reaction.
(f) construct redox equations using the relevant half-equations.
(g) predict qualitatively how the value of an electrode potential varies with the concentration of
the aqueous ion.
(h) state the possible advantages of developing other types of cell, e.g. the H2/O2 fuel cell and
improved batteries (as in electric vehicles) in terms of smaller size, lower mass and higher
voltage.
(i) state the relationship, F = Le, between the Faraday constant, the Avogadro constant and the
charge on the electron.
(j) predict the identity of the substance liberated during electrolysis from the state of electrolyte
(molten or aqueous), position in the redox series (electrode potential) and concentration.
(k) calculate:
(i) the quantity of charge passed during electrolysis.
(ii) the mass and/or volume of substance liberated during electrolysis, including those in the
electrolysis of H2SO4(aq), Na2SO4(aq).
(l) describe the determination of a value of the Avogadro constant by an electrolytic method.
21.1 Standard Electrode Potential
Electrode potentials and half-cells

1) i. When a metal, M is immersed into water, there is a tendency that it will lose
electrons and enter the water as metal ions, Mª⁺. Soon, the water becomes a
solution of the metal ions. This leaves the electrons on the metal and the
metal becomes more and more negative.
M(s) → Mª⁺(aq) + ae⁻ , electrons are left behind the metal
ii. The positive metal ions in the solution will be attracted towards the negative
metal. Eventually some will accept the electrons and re-form the metal.
Mª⁺(aq) + ae⁻ → M(s) , ions from solution deposited

2) When the rate of these two reactions becomes equal, an equilibrium is

established. At this equilibrium, the metal goes into the solution at a rate exactly
same as the ions depositing.
Mª⁺(aq) + ae⁻ ⇌ M(s)

3) Different metals will have different tendencies of doing so. Some will
lose electrons more readily than others. Reactive metals like magnesium prefer
to stay as ions, therefore the position of equilibrium lies further to the left.
Oppositely, unreactive metals like copper prefer to stay as metals, therefore the
position of equilibrium lies further to the right.

Mg²⁺(aq) + 2e⁻ ⇌ Mg(s)

Cu²⁺(aq) + 2e⁻ ⇌ Cu(s)

4) This arrangement of a metal dipping into a solution of its ions is called a

half-cell. The metal in a half-cell is called an electrode.

5) Since there is a difference in charge between the

negative metal and the positive metal ion solution, a
potential difference exists between them. This
potential difference is called the electrode potential, E.
Electrode potential is measured in volts, V.
6) Electrode potential is also a numerical method to express the tendency of a
metal to form ions.

7) The bigger the difference between the negativeness and positiveness, the greater
the electrode potential. However, this electrode potential is impossible to
measure.

8) However, the difference of electrode potentials between two half-cells is

measurable. This can be done by connecting a wire between the two electrodes
with a voltmeter between them.

9) Hence, to standardise, a standard half-cell must be chosen as the reference

electrode so that all electrode potentials measured are relative to this.

10) This standard half-cell is called the standard hydrogen electrode, SHE.

Standard hydrogen electrode, SHE

1) A standard hydrogen electrode has hydrogen gas in equilibrium with hydrogen

ions. The electrode potential of this half-cell is taken as 0 V.
2H⁺(aq) + 2e⁻ ⇌ H2(g) E=0V

2) Since hydrogen is not a metal, platinum foil covered in porous platinum is used
as the electrode. Platinum also catalyses the set up of the equilibrium.

3) Hydrogen gas at 100 kPa is bubbled over the platinum. On the surface of the
platinum, the equilibrium is set up. The concentration of hydrogen ions is
at 1 mol dm⁻³.
Standard electrode potential, E°

1) Standard electrode potential, E° is the e.m.f. of a cell when a half-cell is connected to

a standard hydrogen electrode under standard conditions.

2) The standard conditions are:

i. A pressure of 100 kPa(approximately atmospheric pressure).
ii. A temperature of 298 K or 25 °C.
iii. The ions at a concentration of 1.0 mol dm⁻³.

3) A standard condition is required because all these factors will affect the position
of equilibrium of the reaction, therefore the magnitude of E° will also be
affected.

4) The standard electrode potential of a cell can be measured by connecting a

half-cell to a standard hydrogen electrode like this:

Note:
1) A high resistance voltmeter is used so that
no current flows through the external
circuit and the maximum voltage(the
e.m.f.) can be recorded.
2) A salt bridge physically separates the
half-cells but allows the passage of
electricity between the electrodes. It
contains ions that does not react with the
solution.
2) 1 bar = 100 kPa ≈ 1 atm

5) Recall that electrode potential measures the tendency of a metal to lose its
electrons. Standard electrode potential compares this tendency with the
tendency of hydrogen to release its electrons.

6) i. A negative value of E° implies that the metal loses electrons more readily than
hydrogen does. Therefore the position of equilibrium lies further to the left.
ii. A positive value of E° implies that the metal loses electrons less readily than
hydrogen does. Therefore the position of equilibrium lies further to the right.
Mª⁺(aq) + ae⁻ ⇌ M(s) ; E° = negative
2H⁺(aq) + 2e⁻ ⇌ H2(g) ; E° = 0 V
Nⁿ⁺(aq) + ne⁻ ⇌ N(s) ; E° = positive
7) Remember that standard electrode potential is all about comparing. A positive
E° does not mean the position of equilibrium is exactly at the right. It is further
to the right compared to the position of equilibrium of SHE.

8) i. The bigger the negative value, the further the position of equilibrium is to the
left and the more reactive that metal is.
ii. The bigger the positive value, the further the position of equilibrium is to the
right, and the less reactive that metal is.

The electrochemical series

1) The electrochemical series is built up by arranging various redox equilibria in

order of their standard electrode potentials.

2) The figures above show some common redox equilibria arranged according to
their standard electrode potentials. The full list can be found in the Data Booklet.

3) From the top to the bottom, the position of equilibrium shifts from right to left.
This is because the value of E° changes from the most positive to the most
negative.

4) This implies that the ease of losing electrons by the element increases
from top to bottom(or the ease of gaining electrons by the ion decreases
from top to bottom).

5) i. Ions at the top(with more positive E° value) gain electrons and get reduced
more readily, hence they are good oxidising agents.
ii. Elements(metals) at the bottom(with more negative E° value) lose electrons
and get oxidised more readily, hence they are good reducing agents.
21.2 Measuring Standard Electrode Potential
The big picture

1) The standard electrode potential of the following system will be considered:

i. A metal/metal ion half-cell with SHE.
ii. A non-metal/non-metal ion half-cell with SHE.
iii. An ion/ion(with different oxidation states) half-cell with SHE.
iv. The combination of the above three half-cells.

Metal/metal ion half-cell

+ -
1) Take magnesium as an example of a metal.
The equilibrium set up on both electrodes
are:
Mg²⁺(aq) + 2e⁻ ⇌ Mg(s)
2H⁺(aq) + 2e⁻ ⇌ H2(g)

2) From the voltmeter reading, the E°cell = 2.34 V. Thus, the standard electrode
potential of Mg/Mg²⁺ half-cell is -2.34 V.

3) i. Cathode, which is the positive terminal is

platinum of the H2/H⁺ half-cell. This is because
more electrons are being accepted here due to
the position of equilibrium of the H2/H⁺ being
further to the right.
ii. Anode, which is the negative terminal is
magnesium of the Mg/Mg²⁺ half-cell. This is
because more electrons are being released here due to the position of
equilibrium of the Mg/Mg²⁺ half-cell being further to the left.

4) The full cell can be represented using a cell

diagram. A simple cell diagram is as
shown beside.
Note:
i. The positive electrode is always written on the left
side.
ii. The species with lowest oxidation state is written
next to the inert electrode.
5) A negative E° value implies that magnesium loses electrons more readily
than hydrogen does.

5) If magnesium is replaced by copper, the value of E° will be +0.34 V. Copper of

Cu/Cu²⁺ half-cell will be the positive terminal while platinum of H2/H⁺ half-cell
will be the negative terminal.

6) A positive E° value implies that copper ions gain electrons more readily
than hydrogen ions does.

Non-metal/non-metal ion half-cell

1) Take chlorine as an example of a

non-metal. The equilibrium set up
on both electrodes are:
2Cl⁻(aq) + 2e⁻ ⇌ Cl2(g)
2H⁺(aq) + 2e⁻ ⇌ H2(g)
2) Since chlorine is not a metal, the electrical contact with the solution is made by
using platinum as the electrode(same as SHE).

3) From the voltmeter reading, the E°cell = 1.36 V. Thus, the standard electrode
potential of Cl2/Cl⁻ half-cell is +1.36 V.

4) i. Cathode, which is the positive terminal is platinum of the Cl2/Cl⁻ half-cell.

This is because more electrons are being accepted here due to the position of
equilibrium of the Cl2/Cl⁻ being further to the right.
ii. Anode, which is the negative terminal is platinum of the H2/H⁺ half-cell. This
is because more electrons are being released here due to the position of
equilibrium of the H2/H⁺ half-cell being further to the left.

5) A positive E° value implies that chloride ions gain electrons more readily
than hydrogen ions does.

6) The cell diagram of this cell is:

Ion/ion half-cell

1) Two different ions of the same

element with two different
oxidation states can also be
used as a half-cell. Take
iron(II) and iron(III) ions as
example. The equilibrium set up on both electrodes are:
Fe³⁺(aq) + e⁻ ⇌ Fe²⁺(aq)
2H⁺(aq) + 2e⁻ ⇌ H2(g)

2) Since there is no solid metal as an electrode, electrical contact the solution is

made by using platinum as the electrode.

3) From the voltmeter reading, the E°cell = 0.77 V. Thus, the standard electrode
potential of Fe²⁺/Fe³⁺ half-cell is +0.77 V.

4) i. Cathode, which is the positive terminal is platinum of the Fe²⁺/Fe³⁺ half-cell.

This is because more electrons are being accepted here due to the position of
equilibrium of the Fe²⁺/Fe³⁺ being further to the right.
ii. Anode, which is the negative terminal is platinum of the H2/H⁺ half-cell. This
is because more electrons are being released here due to the position of
equilibrium of the H2/H⁺ half-cell being further to the left.

5) A positive E° value implies that iron(III) ions gain electrons more readily
than hydrogen ions does.

6) The cell diagram of this cell is:

Combination of half-cells

1) In fact, the SHE shown in previous examples can be replaced by other

half-cells.

2) When this happens, the standard cell potential, E°cell will also change, the new
E°cell is simply the difference between the E° values of the two half-cells.
E°cell = E°(bigger value) - E°(smaller value)
3) For example, when Zn/Zn²⁺ half-cell is connected
to Cu/Cu²⁺ half-cell, the equilibrium set up on
both electrodes are:
Zn²⁺(aq) + 2e⁻ ⇌ Zn(s) ; E° = -0.76 V
(-) (+)

Cu²⁺(aq) + 2e⁻ ⇌ Cu(s) ; E° = +0.34 V

4) From the voltmeter reading, the E°cell = 1.10 V.

This can also be calculated, using:
E°cell = 0.34 - (-0.76) = 1.10 V

4) i. Cathode, which is the positive terminal is copper of the Cu/Cu²⁺ half-cell.

This is because more electrons are being accepted here due to the position of
equilibrium of the Cu/Cu²⁺ being further to the right.
ii. Anode, which is the negative terminal is platinum of the Zn/Zn²⁺ half-cell.
This is because more electrons are being released here due to the position of
equilibrium of the Zn/Zn²⁺ half-cell being further to the left.

20.3 Using E° Values

The usage of E° values

1) The value of standard electrode potential, E° can be used in some ways:

i. To predict standard cell potentials, E°cell.
ii. To determine the direction of electron flow.
iii. To predict the feasibility of reactions.
iv. To determine the strength of reducing and oxidising agents.

Predicting standard cell potentials, E°cell

1) The standard cell potential, E°cell of a cell consisting of two half-cells can be
predicted by connecting them together using wires with a voltmeter.

2) i. Find from the Data Booklet the required equilibrium equation.

ii. Copy down the equilibrium equations and their corresponding E° values.
iii. Use the formula E°cell = E°(bigger value) - E°(smaller value).
Determining the direction of electron flow

1) When the high-resistance voltmeter of a cell is removed,

electrons will flow from one cell to another. The electron
will flow from the half-cell with more electrons(anode)
to the half-cell with less electrons(cathode).

2) For example, if the voltmeter in the Zn/Zn²⁺ half-cell and Cu/Cu²⁺ half-cell is
removed, electrons will flow from zinc electrode to copper electrode.

3) Due to the fact that the system is equilibrium, the decrease in electron
concentration in the Zn/Zn²⁺ equilibrium will be accompanied by some
changes. The same goes to the increase in electron concentration in Cu/Cu²⁺
half-cells. This comes from Le Chatelier's principle.

4) If the electrons continue to flow, the position of equilibrium keeps shifting,

eventually producing a one-way reaction.
Zn(s) → Zn²⁺(aq) + 2e⁻ , releases electrons to the Cu/Cu²⁺ half-cell
Cu²⁺(aq) + 2e⁻ → Cu(s) , accepts electrons from the Zn/Zn²⁺ half-cell
...combining these two equations:
Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s)

5) Electrons will always flow from the half-cell with lower(more negative or
less positive) E° value to the half-cell with higher(less negative or more
positive) E° value.
6) Two more examples:

e⁻

Predicting the feasibility of reactions(two methods)

1) Reactions with positive E° value is said to be thermodynamically feasible.

2) Sometimes this prediction fails because:

i. the actual conditions of the reaction are not standard conditions.
ii. the reaction has high activation energy.

3) Remember:
i. E° value gives no information about the reaction rates.
ii. E° value applies to standard conditions only.

4) i. If you are given an equation, split the equation into two half-equations, the
find the corresponding E° values from the Data Booklet.
ii. Add the two E° values together and determine whether the sum is positive
or negative.
iii. Reverse the equation may be necessary, remember to reverse the sign too.
5) Examples:

6) Alternatively, it can also be predicted by looking at the reactants and products

of the equation.

7) Example 1: Will oxygen oxidise iron(II) hydroxide to iron(III) hydroxide under

alkaline conditions?
i. Find from the Data Booklet the equations involving the reactants and products
stated and write down their corresponding E° values.

ii. Determine the direction of electron flow. Remember that electrons flow from
the half-cell with more negative E° value to the half-cell with more positive E°
value.
iii. Determine the shift of position of equilibrium, and see whether it tallies with
the reactants and products.

e⁻
 iv. From the direction of electron flow and shift of equilibrium, we can deduce
that:
- iron(II) hydroxide will be oxidised to iron(III) hydroxide because the position
of equilibrium of first reaction shifts to the left.
- oxygen will accept electrons from the first reaction and will be reduced to
hydroxide ions because the position of equilibrium of second reaction shifts
to right.

8) Example 2: Will chlorine oxidise manganese(II) ions to manganate(VII) ions?

i. Find from the Data Booklet the equations involving the reactants and products
stated and write down their corresponding E° values.

ii. Determine the direction of electron flow. Remember that electrons flow from
the half-cell with more negative E° value to the half-cell with more positive E°
value.
iii. Determine the shift of position of equilibrium, and see whether it tallies with
the reactants and products.
e⁻

iv. From the direction of electron flow and shift of equilibrium, we can deduce
that:
- manganese(II) ions will not be oxidised to manganate(VI) ions because if
it were to occur the position of equilibrium of first reaction will shift to the
left. However, it shifts to the right because the first reaction has a more
positive E° value.
- chlorine will not be reduced to chloride ions because if it were to occur the
position of equilibrium of the second reaction will shift to the right.
However, it shifts to the left because the second reaction has a more negative
E° value.
Determining the strength of oxidising and reducing agents

1) From the last example, the scenario can also be interpreted as:
i. Chlorine is a weaker oxidising agent than manganate(VI) ion, hence it will
not oxidise manganese(II) ion to manganate(VI) ion.
ii. Manganese(II) ion is a weaker reducing agent than chloride ion, hence it will
not reduce chlorine to chloride ion.

2) From the second last example, the scenario can also be interpreted as:
i. Iron(II) hydroxide is a stronger reducing agent than hydroxide ion, hence it
will reduce oxygen to hydroxide ion.
ii. Oxygen is a stronger oxidising agent than iron(III) hydroxide, hence it will
oxidise iron(III) hydroxide to iron(III) hydroxide.

Effect of temperature, pressure and concentration on E° value

1) Since redox equilibria are equilibria, a change in temperature, concentration

and pressure will have an effect on its position of equilibrium. This will also
affect the value of E° because E° indicates the position of equilibrium of a
redox equilibrium.

2) i. If a change causes the position of equilibrium to shift to the right, the value
of E° increases.
ii. If a change causes the position of equilibrium to shift to the left, the value of
E° decreases.

21.4 Cells and Batteries

Rechargable and non-rechargeable cells

1) Batteries are electrochemical cells used as portable sources of electricity.

2) i. Primary cells cannot be recharged and are discarded once the supply of
electric current decreases. This happens when the concentration of reactants
becomes too low.
ii. Secondary cells can be recharged over and over again. This involves
converting the products back to the reactants produced when delivering the
current by electric current.
Dry cells

1)

Lead-acid accumulator

1)

Hydrogen-oxygen fuel cells

Electric cars
21.5 Quantitative Electrolysis
E° value in electrolysis

1) Recall that the selective discharge of ions during electrolysis is affected by:
i. the position of ions in the electrochemical series.
ii. the concentration of ions.

2) Cations lower in the electrochemical series will be

selectively discharged(reduced). This is because they
have a more positive E° value and hence it favours
reduction more.

3) Cations with higher concentration will be selectively

discharged(reduced). This is because the value of E°
becomes more positive as the concentration of ions
increases. A more positive E° favours reduction.

Faraday's laws of electrolysis

1) The quantity of charge,Q passed during electrolysis is given by this equation. Q

is measured in Coulombs, C
where I = Current/A
Q = It t = Time/s

2) Faraday's first law of electrolysis states that the mass of a substance liberated during
electrolysis is directly proportional to the quantity of charge passed through
during electrolysis.

3) Faraday's second law of electrolysis states that the number of Faradays required to
discharge one mole of ion at an electrode equals to the number of charges on
the ion.

4) Faraday, F is the amount of charge carried by one mole of electrons.

1 electron → 1.60 x 10⁻¹⁹ C
6.02 x 10²³ electrons → 96500 C
 Therefore, 1 F = 96500 C

5) Calculation examples:

Determining the value of Avogadro's constant, L by means of electrolysis

1) The Avogadro's constant can be determined using electrolysis. This is done by

calculating the charge associated with one mole of electrons. Then, Avogadro's
constant can be calculated using:
charge on one mole of electrons
L=
charge on one electron

2) The charge on one electron is 1.60 x 10⁻¹⁹ C, this is done using physics
calculation.

3) The charge on one mole of electrons is then found from a simple electrolysis
experiment.
4) The procedure is
i. Weigh the pure copper anode and pure copper cathode separately.
ii. Arrange the apparatus as shown. The variable resistor is used to keep the
current constant.
iii. Pass a constant electric current for a measured time interval.
iv. Remove the cathode and anode and wash and dry them with distilled water
and then with propanone.
v. Reweigh the copper cathode and anode

5) The cathode increases in mass because copper is deposited, the anode decreases
in mass because the copper goes into the solution as ions. The decrease in mass
of anode is preferably measured, this is because copper does not always 'stick' to
the cathode very well, resulting in inaccurate gain in mass.

6) Suppose a sample set of experiment data is as shown below:

- Mass of anode at the beginning = 56.53 g
- Mass of anode at the end = 56.40 g
- Mass of copper removed from anode = 0.13 g
- Quantity of charge passed = 408 C

7) i. Cu²⁺(aq) + 2e⁻ → Cu(s)

ii. 0.13 g → 408 C
63.5 g → 63.5 x 408 ÷ 0.14 = 185057.143 C, for two moles of electrons
iii. Therefore, charge on one mole of electrons = 185057.143 ÷ 2
= 99600 C
iv. Therefore, L = 99600 ÷ 1.60 x 10⁻¹⁹ C = 6.2 x 10²³
v. This is a good agreement with the accurate value, 6.02 x 10²³.
CHAPTER 22: Ionic Equilibria
22.1 pH, Ka, pKa and Kw
22.2 Acid-base Titrations
22.3 Buffer Solutions
22.4 Solubility Equilibria

Learning outcomes:

(a) explain the terms pH, Ka, pKa, Kw and use them in calculations.
(b) calculate [H⁺(aq)] and pH values for strong and weak acids and strong bases.
(c) explain the choice of suitable indicators for acid-base titrations, given appropriate data.
(d) describe the changes in pH during acid-base titrations and explain these changes in terms of
the strengths of the acids and bases.
(e) (i) explain how buffer solutions control pH.
(ii) describe and explain their uses, including the role of HCO³⁻ in controlling pH in blood.
(f) calculate the pH of buffer solutions, given appropriate data.
(g) show understanding of, and use, the concept of solubility product, Ksp.
(h) calculate Ksp from concentrations and vice versa.
(r) show understanding of the common ion effect.
22.1 pH, Ka, pKa and Kw
The ionic product of water, Kw

1) Water is able to act as an acid as well as a base. Therefore whenever liquid

water is present, the following equilibrium occurs.
2H2O ⇌ H3O⁺ + OH⁻

Or the more simplified version(Note that H⁺ ≡ H3O⁺):

H2O ⇌ H⁺ + OH⁻

2) Therefore the ionic product of water is defined as:

3) It means that the product of hydrogen and hydroxide concentrations at a

certain temperature is constant, this is true no matter the water is pure or
impure.

4) At 25 °C, the value of Kw is 1.00 x 10⁻¹⁴ mol² dm⁻⁶.

5) Since the above reaction is an endothermic reaction, the value of Kw increases

with increasing temperature. At 100 °C, the value is 5.13 x 10⁻¹³ mol² dm⁻⁶.

pH of a substance

1) pH of a substance is defined as:

2) To calculate the pH of pure water at 25 °C:

i. Since the water is pure, the hydrogen ion concentration must be equal to the
hydroxide ion concentration. For every hydrogen ion formed, there is a
 hydroxide ion formed as well.
ii. So, the expression for Kw can be simplified to:
[H⁺]² = 1.00 x 10⁻¹⁴ ; since [H⁺] = [OH⁻]
[H⁺] = 1.00 x 10⁻⁷
iii. Therefore the pH of water is given by
pH = -log(1.00 x 10⁻⁷)
pH = 7.00
iv. This implies that at 24 °C, pH 7.00 is the neutral point of water, equal
amounts of hydrogen and hydroxide ions are present.

3) i. At 100 °C, the pH of pure water is 6.14. This does not mean the water is
more acidic at higher temperature.
ii. pH of 6.14 is the neutral point of water at 100 °C, there are still equal
amounts of hydrogen and hydroxide ions present.

Strong and weak acids

1) i. A strong acid ionises completely in the presence of water.

HA + H2O → H3O⁺ + A⁻
ii. Therefore the pH of strong monoprotic acid can be calculated using:
pH = -log[H3O⁺]
Since the acid ionises completely, [H3O⁺] = [HA]
pH = -log[HA]

2) i. A weak acid ionises partially in the presence of water.

HA + H2O ⇌ H3O⁺ + A⁻
ii. The pH of a weak acid is calculated using the acid dissociation constant, Ka.

Acid dissociation constant, Ka

1) i. For the dissociation of a weak acid, Kc can be written as:

ii. However, the concentration of water is fairly constant. This is because at any
one time, only about 1 % of the HA has reacted.
iii. Therefore a new equilibrium constant, Ka is defined as:

or
2) i. Ka can be used to measure the strength of weak acids.
ii. A stronger acid has the position of equilibrium further to the right,
therefore a higher Ka value.
iii. A weaker acid has the position of equilibrium further to the right, therefore
a lower Ka value.

3) To make the comparison easier to see, the strength of acids is measured on the
pKa scale. Just like pH, pKa is defined as:

4) The numbers now become:

5) Conclusion:
i. The stronger the acid, the higher the Ka and the lower the pKa.
ii. The weaker the acid, the lower the Ka and the higher the pKa.

Calculations on pH

1) To calculate the pH of a strong acid:

i. A strong acid ionises completely in the presence of water.
HA + H2O → H3O⁺ + A⁻
ii. Therefore the pH of a strong monoprotic acid can be calculated using:
pH = -log[H3O⁺]
 Since the acid ionises completely, [H3O⁺] = [HA]
pH = -log[HA] ; if [HA] is given
iii. For a diprotic acid, [H2A] = 2[H3O⁺]
iv. For a triprotic acid, [H₃A] = 3[H3O⁺]

2) To calculate pH of a weak acid:

i. A weak acid ionises partially in the presence of water.
HA + H2O ⇌ H3O⁺ + A⁻
ii. For example, if you have c mol dm⁻³ of weak acid, HA. Do a calculation to
find the concentration of H3O⁺ and A⁻ at equilibrium.

iii. Important approximations when calculating pH of a weak acid:

- So little acid has ionised that the concentration of HA at equilibrium is the
same as the initial concentration. That is, c - x ≈ c.
- If the acid is pure, then the concentration of hydrogen ions and the negative
ions are the same. That is, [H3O⁺] = [A⁻] = x.
iv. Then use the formula for Ka to obtain the concentration of hydrogen ions,
given the value of Ka.
v. Then use the pH formula to calculate the pH.

3) To calculate the pH of a strong base:

i. A strong base ionises completely in the presence of water.
B + H2O → BH⁺ + OH⁻
ii. Since the base ionises completely, [OH⁻] = [B] ; if [B] is given
iii. Obtain the concentration of hydrogen ions from the expression of Kw. This is
valid because the product of [H⁺] and [OH⁻] is constant at constant
temperature.
iv. Then use the pH formula to calculate its pH.
v. Alternatively, a quantity known as pOH can be calculated where
pOH = -log[OH⁻]
Then use the fact that pH + pOH = 14 to calculate its pH.

[ Note: Calculation involving weak bases is not required. ]

22.2 Acid-base Titrations
Titration curves

1) Titration curves or pH curves are curves that show the pH changes during
an acid-base titration.

2) Titration curve of a strong acid and strong base titration, take

hydrochloric acid and sodium hydroxide as an example:
i. Running the acid into alkali:
- pH changes by a small amount until the equivalence point, that is, the
point where the solutions have been mixed in exactly the right proportions
according to the equation.
- This is followed by a sharp decrease in pH when small amount of acid is
added.

ii. Running the alkali into acid:

- This is the same as above except the curves starts at pH 0, because the
curve shows the pH in the conical flask.

3) Titration curve of a strong acid and weak base titration, take hydrochloric
acid and ammonia as an example:
 i. Running the acid into alkali:
- The curve starts at pH 12 because a weak base is present.
- Initially, the pH falls rapidly. As more acid is added, the curve becomes less
steep because a buffer solution composed of excess ammonia and
ammonium chloride is set up. Buffer solutions resist changes pH when small
amount of acid is added.
- The equivalence point now is a bit acidic.
- When excess acid is added, the curve is the same as before.

ii. Running the alkali into acid:

- The beginning of curve is the same as before.
- After the equivalence point(which is also a bit acidic), the pH changes
by a small amount. This is because a buffer solution composed of excess
ammonia and ammonium chloride is set up. Buffer solutions resist changes
in pH when small amount of alkali is added.

4) Titration curve of a weak acid and strong base titration, take ethanoic
acid and sodium hydroxide as an example:
i. Running the acid into alkali:
- The beginning of curve is the same as before.
- After the equivalence point(which is a bit alkaline), the pH changes by a
small amount. This is because a buffer solution composed of excess sodium
 ethanoate and ethanoic acid is set up. Buffer solutions resists pH changes
when small amount of acid is added.

ii. Running the alkali into acid:

- The curve starts at pH 3 because a weak acid is present.
- Initially, the pH increases rapidly. As more alkali is added, the curve becomes
less steep because a buffer solution composed of excess sodium ethanoate
and ethanoic acid is set up. Buffer solutions resist changes pH when small
amount of alkali is added.
- The equivalence point now is a bit alkaline.
- When excess alkali is added, the curve is the same as before.

5) Titration curve of a weak acid and weak base titration, take ethanoic acid
and ammonia as an example:
i. Running the acid into alkali
- The curve starts at pH 12 because a weak base is present.
- Initially, the pH falls rapidly. As more acid is added, the curve becomes less
steep because a buffer solution composed of excess ammonia and
ammonium ethanoate is set up. Buffer solutions resist changes pH when
small amount of acid is added.
- There is no sharp decrease in pH at any volume.
 ii. Running the alkali into acid
- The curve starts at pH 3 because a weak acid is present.
- Initially, the pH increases rapidly. As more alkali is added, the curve becomes
less steep because a buffer solution composed of excess ammonium
ethanoate and ethanoic acid is set up. Buffer solutions resist changes pH
when small amount of alkali is added.

6) Titration curve of a polyprotic acid and base titration, take ethanedioic

acid and sodium hydroxide as an example:
i. Running the alkali into acid:
- Ethanedioic acid is a diprotic acid, it donates the two protons in two stages.
This is because one proton is more easier to remove than the other.

Stage 1:

Stage 2:
 - The curve will therefore show two sharp increase in pH.

Acid-base indicator

1) An indicator is a substance that changes colour as the pH of the solution which

it dissolves changes.

2) In an acid-base titration, an indicator is used to mark the end point of the

titration, that is, the point where the indicator changes colour.

3) Most indicators are weak acids. They have an acid colour and a base colour.

4) Consider a general indicator with the formula HIn. HIn has a different colour
from In⁻. The colour of HIn is called the acid colour while the colour of In⁻ is
called the base colour.
HIn ⇌ H⁺ + In⁻
i. When acid is added, the equilibrium position shifts to the left due to the
increasing concentration of H⁺ ions. The indicator exists predominantly as
HIn. Hence, the solution shows the acid colour.
ii. When base is added, the equilibrium position shifts to the right due to the
removal of H⁺ ions. The indicator exists predominantly as In⁻. Hence, the
solution shows the base colour.

5) Take methyl orange as an example, it has an acid colour of red and a base
colour of yellow.

i. When acid is added, the equilibrium position shifts to the left and the solution
looks red.
ii. When base is added, the equilibrium position shifts to the right and the
solution looks yellow
Importance of pKIn

1) Since the indicator is a weak acid, an expression of Ka can be written for it.
However, the Ka now is called KIn.

2) As acid/base is added, the colour changes. At half-way through the colour

changes, there will be equal amount of HIn and In⁻ present. The equilibrium
expression now becomes:

3) This means that the end point depends entirely on the pKIn of the indicator. At
pH = pKIn, the indicator is changing its colour.

4) However, the indicator usually changes its colour over a range of pH, usually
around pKIn ± 1, this is called the pH range of am indicator.

4) Some common examples:

Selecting a suitable indicator for titration

1) An indicator should be chosen such that it changes colour close to the

equivalence point of the titration to give an accurate titration result.

2) The indicator therefore should have a pH range close to the equivalence point
of the titration.
3) A guide to choose a suitable indicator:

Finding pKa from titration curves

1) Suppose during an acid-base titration, 25 cm³ of alkali is required to neutralise

a weak acid. Therefore at half-neutralisation, half-volume of the alkali has been
added, that is 12.5 cm³.

2) Half of the acid has been neutralised and half of the salt has been formed.
Therefore, [HA] = [A⁻].

3) According to the formula, log([HA]/[A⁻]) = 1 and pKa = pH.

4) Conclusion is, pKa is the pH of the solution at half-neutralisation.

22.3 Buffer Solutions

What is a buffer solution?

1) A buffer solution is a solution whose pH does not change significantly when small
amount of acid or base is added to it.

2) Buffer solutions should therefore contain:

i. large amount of acid to react with the base added.
 ii. large amount of base to react with the acid added.

3) Since the added acid and base can be removed, the pH does not change
significantly.

4) These conditions can be achieved if the solution contains a mixture of a

weak acid and its conjugate base, or a weak base with its conjugate
acid.

5) There are two types of buffer solutions, named acidic buffer solution and
alkaline buffer solution.

Acidic buffer solution

1) An acidic buffer solution is acidic and can be made by mixing a weak acid
and its conjugate base together. Take ethanoic acid and ethanoate ion as
an example.

2) Sodium ethanoate is added to ethanoic acid. Sodium ethanoate dissociates

completely according to the equation:
CH3COONa → CH3COO⁻ + Na⁺
...while ethanoic acid dissociates partially according to the equation:
CH3COOH ⇌ CH3COO⁻ + H⁺
3) The presence of ethanoate ions causes the equilibrium position to shift to the
left. The solution now contains:
i. large reservoir of ethanoic acid molecules.
ii. large reservoir of ethanoate ions.
iii. enough hydrogen ions to make the solution acidic.

4) When acid is added:

i. The hydrogen ions from the acid added will react with the large reservoir
of ethanoate ions.
H⁺ + CH3COO⁻ → CH3COOH
ii. The extra hydrogen ions are removed, and the pH drops very little.

5) When base is added:

i. The hydroxide ions from the base added will react with the large
reservoir of ethanoic acid molecules.
OH⁻ + CH3COOH → CH3COO⁻ + H2O
 ii. The extra hydroxide ions are removed, and the pH increases very little.

Alkaline buffer solution

1) An alkaline buffer solution is alkaline and can be made by mixing a weak

base and its conjugate acid together. Take ammonia and ammonium ion
as an example.

2) Ammonium chloride is added to ammonia. Ammonium chloride dissociates

completely according to the equation:
NH4Cl → NH4⁺ + Cl⁻
...while ammonia ionises partially according to the equation:
NH3 + H2O ⇌ NH4⁺ + OH⁻
3) The presence of ammonium ions causes the equilibrium position to shift to the
left. The solution now contains:
i. large reservoir of ammonia molecules.
ii. large reservoir of ammonium ions.
iii. enough hydroxide ions to make the solution alkaline.

4) When acid is added:

i. The hydrogen ions from the acid added will react with the large
reservoir of ammonia molecules.
H⁺ + NH3 → NH4⁺
ii. The extra hydrogen ions are removed, and the pH drops very little.

5) When base is added:

i. The hydroxide ions from the base added will react with the large
reservoir of ammonium ions.
OH⁻ + NH4⁺ → NH3 + H2O
ii. The extra hydroxide ions are removed, and the pH increases very little.

Calculating the pH of buffer solutions

1) For an acidic buffer solution:

CH3COOH ⇌ CH3COO⁻ + H⁺
i. Make the following assumptions:
- Concentration of ethanoate ions is equal to the concentration of
sodium ethanoate added. This is done by ignoring the negligible amount
of ethanoate ions coming from the dissociation of ethanoic acid.
 - Concentration of ethanoic acid is equal to its original
concentration. This is done by ignoring the negligible amount of ethanoic
acid dissociated.
ii. The Ka expression of ethanoic acid now becomes:

iii. Given the value of Ka of ethanoic acid, concentration of hydrogen ions and
hence the pH of the buffer solution can be found.

2) For an alkaline buffer solution:

NH3 + H2O ⇌ NH4⁺ + OH⁻
i. Adjust the point view to the ammonium ion rather than ammonia.
This is possible because ammonium ions are weak acids. Therefore:
NH4⁺ ⇌ NH3 + H⁺
ii. Make the following assumptions:
- Concentration of ammonium ions is equal to the concentration of
ammonium chloride added. This is done by ignoring the negligible
amount of ammonium ions coming from the ionisation of ammonia.
- Concentration of ammonia is equal to its original concentration.
This is done by ignoring the negligible amount of ammonia ionised.
iii. The Ka expression of ammonium ion now becomes:

iv. Given the value of Ka of ammonium ion, concentration of hydrogen ions and
hence the pH of the buffer solution can be found.
Importance of buffer solutions in biological systems

1) Most biological reactions(especially those involving enzymes) are very sensitive

to pH, since enzymes can only function within a narrow range of pH.

2) For example, if the pH of human blood(pH 7.4) is changed by as little as 0.4

unit, it could prove fatal.

3) There are two important buffer systems in the human blood:

i. The carbonic acid/hydrogen carbonate system.
ii. The phosphate system.

4) The carbonic acid/hydrogen carbonate system:

i. The following equilibrium is involved:
H2CO3 ⇌ H⁺ + HCO3⁻
ii. When a little acid is added:
H⁺ + HCO3⁻ → H2CO3
iii. When a little base is added:
OH⁻ + H2CO3 → HCO3⁻ + H2O

5) The phosphate system:

i. The following equilibrium is involved:
H2PO4⁻ ⇌ HPO4²⁻ + H⁺
ii. When a little acid is added:
H⁺ + HPO4²⁻ → H2PO4⁻
iii. When a little base is added:
OH⁻ + H2PO4⁻ → HPO4²⁻ + H2O
22.4 Solubility Equilibria
Solubility product, Ksp

1) Solubility product, Ksp is the product of the concentrations of each ion in a

saturated solution of a sparingly soluble salt at 298 K, raised to the power of
their relative concentrations.

2) For any so called 'insoluble salt', a tiny amount of it do dissolve in water.

3) i. Solubility product only apply if the solution is in equilibrium with its solid, in
other words, the solution is saturated.
ii. It means that in a saturated solution at 298 K, when the concentrations of the
ions are multiplied together, the value is the solubility product.

4) The higher the value of Ksp, the more soluble the salt is.

5) Solubility product can be used to predict precipitation:

i. If the product of the concentrations of ions is less than the solubility product,
the solution is not saturated, no precipitate will be formed.
ii. If the product of the concentrations of ions is equal to the solubility product,
the solution is saturated, no precipitate is formed yet.
iii. If the product of the concentrations of ions is more than the solubility
product, the solution is saturated, precipitation occurs to reduce the
concentrations to a value equal to the solubility product.
Calculations on solubility product

1) To calculate solubility product from solubility of ions:

2) To calculate the solubility of ions from the solubility product

Common ion effect

1) Consider the equilibrium of barium sulfate and its ions:

BaSO4(s) ⇌ Ba²⁺(aq) + SO4²⁻(aq)
If sulfuric acid, H2SO4 is added, the concentration of sulfate ions increases and
the position of equilibrium shifts to the left. More precipitate is formed and
barium sulfate becomes less soluble.
2) The common ion effect is therefore the reduction in the solubility of a dissolved
salt by adding a solution of a compound which has an ion in common with the
dissolved salt, this often results in precipitation.

3) The solubility of an ionic compound in aqueous solution containing a common

ion is less than its solubility in water.

Calculations on common ion effect

1) To calculate the solubility of an ionic compound in different solvents:

2) To predict precipitation on mixing two solutions:

CHAPTER 23: Reaction Kinetics
23.1 Orders of Reaction and Rate Equations
23.2 Reaction Mechanisms
23.3 Catalysis

Learning outcomes:

(a) explain and use the terms: rate equation, order of reaction, rate constant, half-life of a
reaction, rate-determining step.
(b) construct and use rate equations of the form rate = k[A]m[B]ⁿ (limited to simple cases of
single step reactions and of multistep processes with a rate-determining step, for which m and
n are 0, 1 or 2), including:
(i) deducing the order of a reaction from concentration-time graphs, by the initial rates
method and half-life methods.
(ii) deducing, for zero- and first-order reactions, the order of reaction from concentration-time
graphs.
(iii) verifying that a suggested reaction mechanism is consistent with the observed kinetics.
(iv) predicting the order that would result from a given reaction mechanism (and vice versa).
(c) calculating an initial rate using concentration data. [integrated forms of rate equations are
not required]
(d) (i) show understanding that the half-life of a first-order reaction is independent of
concentration.
(ii) use the half-life of a first-order reaction in calculations.
(e) calculate a rate constant, for example by using the initial rates or half-life method.
(f) devise a suitable experimental technique for studying the rate of a reaction, from given
information.
(g) outline the different modes of action of homogeneous and heterogeneous catalysis, including:
(i) the Haber process.
(ii) the catalytic removal of oxides of nitrogen in the exhaust gases from car engines.
(iii) the catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur
dioxide.
(iv) catalytic role of Fe³⁺ in the I⁻/S2O8²⁻ reaction.

23.1 Orders of Reaction and Rate Equations

Rate Equation

1) The rate of reaction is dependent on the concentration of the reactants.

Doubling the concentration may double or triple the rate of reaction, just to
name a few.

2) A rate equation shows this relationship mathematically.

3) A rate equation can only be obtained experimentally, it cannot be

deduced from the stoichiometric equation and it may not include all reactants
written in the equation.

4) For a general reaction:

A+B→C+D
The rate equation is:

5) k is known as the rate constant, it is only a constant for a given reaction at a

particular temperature. The unit of k depends on the rate equation and orders
of reaction.

6) Note that the unit of rate is mol dm⁻³ s⁻¹ while the units of [A] and [B] are
mol dm⁻³.

Order of reaction

1) The values m and n are known as the orders of reaction. Common values are
0, 1 and 2.

2) The order of reaction with respect to a reactant is the power to which the
concentration of that reactant is raised in the experimentally determined rate
equation.

3) Like rate equations, orders of reaction must be determined experimentally.

4) If a reaction is zero-order with respect to a reactant A:
i. m = 1 and the rate equation becomes rate = k[A]⁰[B]ⁿ
= k[B]ⁿ
ii. The rate of reaction is independent of the concentration of A
because [A]⁰ = 1 and it disappears from the equation. Changing the
concentration of A will not alter the rate of reaction.
iii. - The rate-concentration graph is a horizontal line showing the rate of
reaction does not change.
- The concentration-time graph is a straight line with constant gradient
showing that rate is constant.

5) If a reaction is first-order with respect to a reactant A:

i. m = 1 and the rate equation becomes rate = k[A][B]ⁿ.
ii. The rate of reaction is proportional to the concentration of A. If [A]
increases five times, the rate of reaction will increase five times as well.
iii. - The rate-concentration graph will show a straight line through origin.
- The concentration-time graph will show a curve with constant half-life.

iv. Half-life, t½ is the time taken for the initial concentration of reactant to
decrease to half of its original value.
v. Only a first-order concentration-time graph will show a curve with constant
half-life. That is, t1 = t2 = t3 = t½.
vi. The relationship between half-life and rate constant is given by:

6) If a reaction if second-order with respect to a reactant A:

i. m = 2 and the rate equation becomes rate = k[A]²[B]ⁿ.
ii. The rate of reaction is proportional to the square of concentration
of A. If [A] increases five times, the rate of reaction will increase 5² = 25
 times.
iii. - The rate-concentration graph is a quadratic curve.
- The concentration-time graph is a curve with non-constant half-life.

Deducing orders of reaction

1) Order of reaction must be determined experimentally, it can be deduced by

either graphically or using initial rate experiments.

2) Deducing graphically involves plotting either a rate-concentration graph or

concentration-time graph, and the order of a reaction
may be deduced by looking at the pattern.

3) Using initial rate experiments, the rate of reaction is

measured at the very beginning of the
experiment. This is done by calculating the gradient
of a concentration-time graph at the beginning.

4) A guide to find the order of reaction from the processed data:

Example 1:
Example 2:
23.2 Reaction Mechanisms
Rate-determining step

1) In any chemical change, some bonds are broken and new ones are made. Quite
often, these changes are too complicated to happen in one simple stage. Instead,
the reaction may involve a series of small changes one after the other.

2) A reaction mechanism describes the one or more steps involved in the reaction
in a way which makes it clear exactly how the various bonds are broken and
made.

3) The overall rate of reaction is governed by the rate of the slowest step. The
slow step is therefore called the rate-determining step.

4) For example, the reaction between 2-bromo-2-methylpropane(a tertiary

halogenoalkane) and hydroxide ion happens in two stages.

Stage 1:

Stage 2:
 The overall equation is:

5) In this example, Step 1 is the rate-determining step because the rate of reaction
depends entirely on the rate of this step. Increasing the rate of the already fast
step 2 will not increase the overall rate of reaction.

6) By doing experiments, it can be found that the the rate equation is:
rate = [(CH3)3CBr]
The rate therefore does not depend on the hydroxide ion, which takes part in
the second stage of the reaction.

7) Another example is the reaction between 1-bromoethane(a primary

halogenoalkane) and hydroxide ion. This reaction happens in a single step.

8) The rate equation for this reaction is rate = [CH3CH2Br][OH⁻] because the rate
of reaction depends on these two reactants.

Molecularity of reaction

1) Molecularity of a reaction is the number of species taking part in a (stage of)

reaction.

2) i. In the first example above, Stage 1 has a molecularity of one because only one
species is involved in this stage. Therefore Stage 1 is said to be
unimolecular.
ii. Stage 2 involves two molecules colliding and therefore it has a molecularity of
two. Stage 2 is said to be bimolecular.

3) In the second example, two species are involved, therefore it is a bimolecular

reaction having a molecularity of two.
Order and mechanism

1) Given the rate equation and the orders of reaction, it is possible to deduce the
reaction mechanism and vice versa.

2) i. For example, given:

rate = k[A][B]
And given two possible reaction mechanisms. It can be deduced that
mechanism 2 might be correct. This is because the rate equation tells us both
A and B are involved in the rate-determining step(slow step) of the reaction.
ii. If we know that mechanism 2 is correct. We can deduce that the above rate
equation might be the correct one, since two species are involved in the slow
step.

Mechanism 1 Mechanism 2

3) i. If the rate-determining step is not the first step, for example:

ii. It can be deduced that the rate equation might be

rate = k[A][X]
iii. However, X is only an intermediate. Its concentration can be expressed in
terms of concentrations of A and B, using the fact that the first step is in
equilibrium.
iv. The steps are:
23.3 Catalysis
Phase and physical state

1) A phase is a region of space, throughout which all physical properties of a

material are essentially uniform.

2) Examples of phases:

Heterogeneous catalysis

1) Heterogeneous catalysis involves the use of a catalyst which is in different

phase than the reactants. Most often, the reactants are in gaseous state while
the catalyst is in solid state.

2) In heterogeneous catalysis, the reactants are often adsorbed onto the surface
of the active site of the catalyst.

3) Adsorption means 'sticking onto the surface'. A good catalyst should adsorb
reactants strong enough but not so strong that the products cannot break away.

4) For example, the reaction between ethene and hydrogen is catalysed by nickel
catalyst. Both ethene and hydrogen are gases while nickel is a solid.
i. Ethene molecules are adsorbed on the surface of the nickel. The double
bond between the carbon atoms breaks and the electrons are used to bond it
to the nickel surface.
 ii. Hydrogen molecules are also adsorbed on to the surface of the nickel. When
this happens, the hydrogen molecules are broken into atoms. These can move
around on the surface of the nickel.

iii. If a hydrogen atom diffuses close to one of the bonded carbons, the bond
between the carbon and the nickel is replaced by one between the carbon and
hydrogen.

iv. That end of the original ethene now breaks free of the surface, and eventually
the same thing will happen at the other end.

v. As before, one of the hydrogen atoms forms a bond with the carbon, and that
end also breaks free. There is now space on the surface of the nickel for new
reactant molecules to go through the whole process again.

5) Most heterogeneous catalysts are transition elements or their compounds. This

is because in transition elements, there are empty/partially filled d-orbitals
available for the molecules to be adsorbed to.
Homogeneous catalysis

1) Homogeneous catalysis involves the use of a catalyst which is in the same

phase as the reactants.

2) i. For example, the reaction between persulfate ions and iodide ions:
S2O8²⁻ + 2I⁻ → 2SO4²⁻ + I2
ii. This reaction proceeds very slowly because it involves two negative ions
colliding.
iii. Iron(III) ions, Fe³⁺ is used as a catalyst. It oxidises the iodide ions into iodine
molecules and itself is reduced to iron(II) ions, Fe²⁺.
Fe³⁺ + 2I⁻ → Fe²⁺ + I2
iv. The persulfate ions will oxidise the iron(II) ions into iron(III) ions and itself is
reduced to sulfate ions.
S2O8²⁻ + 2Fe²⁺ → 2SO4²⁻ + 2Fe³⁺
CHAPTER 24: Group IV
24.1 Physical Properties of Group IV Elements
24.2 Group IV Chlorides
24.3 Group IV Oxides
24.3 Relative Stability of +2 and +4 Oxidation States

Learning outcomes:

(a) outline the variation in melting point and in electrical conductivity of the elements and
interpret them in terms of structure and bonding.
(b) describe and explain the bonding in, molecular shape and volatility of the tetrachlorides.
(c) describe and explain the reactions of the tetrachlorides with water in terms of structure and
bonding.
(d) describe and explain the bonding, acid-base nature and thermal stability of the oxides of
oxidation states II and IV.
(e) describe and explain the relative stability of higher and lower oxidation states of the elements
in their oxides and aqueous cations including, where relevant, E values.
24.1 Physical Properties of Group IV Elements
Introduction to Group IV elements

1) Group IV elements are p-block elements with a characteristic outer shell

configuration of ns²np².

2) Group IV elements exist in two different oxidation states, +2 and +4 states.

The +2 state compounds become more stable going down the Group while the
+4 state compounds become less stable going down the Group. The reasons will
be explained later.

Variation in structure

1) Going down the Group, there is a trend of non-metal to semi-metal to metal.

2) Carbon exists in two different allotropes, diamond and graphite(for the structures,
refer to Chapter 5), they are both giant covalent compounds.

3) Silicon and germanium have the same type of structure as diamond. They
are both giant covalent compounds.

4) There are two types of tin:

i. Grey tin or alpha-tin has a giant covalent structure, same as the one diamond
has.
ii. White tin or beta-tin(the more common one) has a distorted 12-co-ordinated
metallic structure with metallic bonds.

5) Lead is a metal and it has a simple 12-co-ordinated metallic structure.

Variation in melting and boiling point

1) From carbon to germanium, the melting

point decreases. This is because going down
the Group, the covalent bond length
increases. Longer bonds have lower bond
energies. Less energy is required to overcome
the covalent bonds, therefore melting point is
lower.

2) i. Tin has a lower melting point than lead. This is because in the solid state,
metallic tin has a distorted structure, resulting the metallic bonds being
less effective. This factor outweighs the larger atomic size of lead.
Therefore, less energy is required to overcome the metallic bond in tin.
ii. Tin has a higher boiling point than lead, this is because in the liquid state,
there is no ordered arrangement between the atoms. The larger atomic
size of lead resulting the metallic bond being longer and weaker.
Therefore, less energy is required to overcome the metallic bond in lead.

Variation in electrical conductivity

1) The electrical conductivity increases down the Group as the nature of the
elements changes from non-metal to semi-metal to metal.

2) i. Carbon(diamond form) does not conduct electricity. This is because

all the outer electrons are used in covalent bonding. Therefore there are no
free and moving electrons to conduct the electricity.
ii. However, carbon(graphite form) conducts electricity. This is because in
the graphite structure each atom donates one electron to a delocalised system
of electrons(for more details, refer to Chapter 5). Therefore there are free electrons
present to conduct the electricity.

3) Silicon and germanium are semi-conductors, whose conductivity is

between that of metals and non-metals.

4) Tin and lead are metals, hence they are good conductors of electricity.
This is because each atom involved in metallic bonding donates electrons into
the sea of delocalised electrons. Therefore free electrons are present to conduct
electricity.
24.2 Group IV Chlorides
Introduction to Group IV chlorides

1) All Group IV chlorides are simple covalent molecules which exist as liquid at
room temperature with the general formula of XCl4, where
X = A Group IV element.

2) All of them have a tetrahedral shape with a bond

angle of 109.5°. A typical example is carbon
tetrachloride:

3) The boiling point of Group IV tetrachlorides increases

down the Group. This is because as the number of
electrons increases, more temporary dipoles can be set up
between the molecules. Hence the van der Waals' forces
of attraction are stronger.

Note: Carbon tetrachloride, CCl4 is an exception.

Reaction with water, H2O(Hydrolysis)

1) i. Carbon tetrachloride does not react with water. If carbon tetrachloride is

added to water, two immiscible layers are formed.
ii. There are two reasons for this:
- Carbon is a small atom cluttered with big chlorine atoms. This
causes the water molecule to have difficulty approaching
the bulky molecule. Even if the water molecule successfully
gets in, the transition state is very cluttered and unstable, the
activation energy is very high.
- Also, there isn't any convenient orbital on the carbon that the lone pair
of the water molecule can attaches itself to.

2) i. Silicon, germanium and tin tetrachlorides(also called silicon(IV)

chloride, germanium(IV) chloride and tin(IV) chloride) hydrolyses in water to
form an oxide and steamy fumes of hydrogen chloride.
XCl4 + 2H2O → XO2 + 4HCl ; where X = Si/Ge/Sn/Pb
ii. Unlike carbon tetrachloride, this is possible because the Group IV atoms are
bigger, the molecules are less bulky.
3) Lead(IV) chloride behaves similarly as silicon, germanium and tin
tetrachlorides. However, the heat released during the reaction would tend to
decompose lead(IV) chloride, PbCl4 to lead(II) chloride, PbCl2.
PbCl4 → PbCl2 + Cl2

4) The hydrolysis reactions become more vigorous going down the Group. This
is because going down the Group, the X-Cl bond becomes longer. A longer
bond has a lower bond energy and it is more easy to be broken.

Relative stability of the oxidation states of Group IV chlorides

1) A fact about Group IV elements is as such:

i. Going down the Group, compounds with a +2
oxidation state Group IV element become more stable.
ii. Going up the Group, compounds with a +4 oxidation
state Group IV element become more stable.

2) This means that the +4 oxidation is less favourable down the Group while the
+2 oxidation state is more favourable down the Group.

3) From carbon to tin, the +4 oxidation state is more stable than +2 oxidation
state. However, for lead, the +2 oxidation is more stable. This is why lead(IV)
chloride decomposes to lead(II) chloride on heating.

24.3 Group IV Oxides

Introduction to Group IV oxides

1) Group IV elements form two types of oxides: monoxide and dioxide. This is
because the elements have two possible oxidation states, +2 and +4.

2) Monoxides include:
i. carbon monoxide, CO
ii. silicon monoxide/silicon(II) oxide, SiO
iii. germanium monoxide, GeO
 iv. tin(II) oxide, SnO
v. lead(II) oxide, PbO

3) Dioxides include:
i. carbon dioxide, CO2
ii. silicon dioxide/silicon(IV) oxide, SiO2
iii. germanium dioxide, GeO2
iv. tin(IV) oxide, SnO2
v. lead(IV) oxide, PbO2

4) i. Carbon monoxide and carbon dioxide is a simple covalent

molecule which exists as a gas at room temperature.

5) i. Silicon monoxide and silicon dioxide has a giant covalent structure(for

more details, refer to Chapter 5).
ii. The difference in structure between carbon dioxide and silicon dioxide is due
to silicon atom being larger. When the atom is larger, the overlapping of p
orbitals to form a π bond is less complete and a π bond as such is very
unstable. So, silicon bonded with the oxygen atoms in such a way that π bonds
are not formed.

6) Germanium monoxide and germanium dioxide have the same structure

as silicon monoxide and silicon dioxide respectively.

7) Tin(II) oxide and tin(IV) oxide have a giant ionic lattice structure with ionic
bonds between the Sn²⁺/Sn⁴⁺ and O²⁻.

8) Lead(II) oxide and lead(IV) oxide have a giant ionic lattice structure with
ionic bonds between the Pb²⁺/Pb⁴⁺ and O²⁻.

Group IV monoxides

1) Carbon monoxide is a slightly acidic oxide which is only slightly soluble in

water. It reacts with hot and concentrated sodium hydroxide, NaOH to give a
solution of sodium methanoate.
CO + NaOH → HCOONa

2) i. Germanium, tin and lead monoxides are amphoteric oxides. They

can act as an acid as well as a base.
 ii. As a base : XO + 2HCl → XCl2 + H2O ; where X = Ge/Sn/Pb
iii. As an acid : XO + 2NaOH → Na2XO2 + H2O ; where X = Ge/Sn/Pb

Group IV dioxides

1) Carbon dioxide is a slight acidic oxide which is only slightly soluble in

water. It reacts with cold sodium hydroxide, NaOH to give either sodium
carbonate or sodium hydrogencarbonate solution, depending on the proportion.
CO2 + 2NaOH → Na2CO3 + H2O or
CO2 + NaOH → NaHCO3

2) Silicon dioxide is weakly acidic. It reacts with hot and concentrated sodium
hydroxide to give sodium silicate. However, it does not react with water due to
the strong covalent bonds need to be broken.
SiO2 + 2NaOH → Na2SiO3 + H2O

3) i. Germanium, tin and lead dioxides are amphoteric oxides. They can
act as an acid as well as a base.
ii. As a base : XO2 + 4HCl → XCl4 + 2H2O ; where X = Ge/Sn/Pb
For germanium and tin dioxides, hot and concentrated hydrochloric acid is
used. However, for lead dioxide, cold hydrochloric acid is used. This is
because lead dioxide will decompose if the temperature increases.
iii. As an acid : XO2 + 2NaOH → Na2XO3 + H2O ; where X = Ge/Sn/Pb
For all reactions, hot and concentrated sodium hydroxide is used.

Thermal stability of Group IV oxides

1) Carbon, silicon and germanium oxides will disproportionate on

heating.
2XO → X + XO2 ; where X = C/Si/Ge

2) Tin and lead monoxide are stable on heating.

3) This reflects the stability of +2 oxidation state of Group IV elements increases

down the Group.

4) All dioxides are stable on heating except lead dioxide(lead(IV) oxide). This
decomposes on heating to give lead(II) oxide and oxygen.
2PbO2 → 2PbO + O2
5) This shows the stability of +4 oxidation state of Group IV elements decreases
down the Group.

24.3 Relative Stability of +2 and +4 Oxidation

States
The stability of +2 and +4 oxidation states

1) i. +4 compounds at the top of the Group is more stable than at the bottom.
ii. +2 compounds at the bottom of the Group is more stable than at the top.

2) For carbon, carbon dioxide(+4) is more stable than carbon monoxide(+2).

Therefore, carbon monoxide is readily oxidised to carbon dioxide, it is a
good reducing agent. For example, it reduces iron(III) ions to iron.
Fe2O3 + 3CO → 2Fe + 3CO2

3) For lead, lead(II) oxide(+2) is more stable than lead(IV) oxide(+4). Therefore,
lead(IV) oxide is readily reduced to lead(II) oxide, it is a good oxidising
agent. For example, lead(II) oxide oxidises hydrochloric acid to chlorine.
PbO2 + 4HCl → PbCl2 + Cl2 + 2H2O

4) Between these extremes, there is a gradual change in stability of the +2

compared with the +4 state.
i. The +4 state of germanium compounds is more stable than the +2 state.
Therefore, germanium(II) compounds are good reducing agents.
ii. The +4 state of tin compounds is slightly more stable than the +2 state.
Therefore, tin(II) compounds are weak reducing agents.

5) This can be interpreted from the E° values of the ions of Group IV elements in
aqueous solutions.
6) i. The more positive the value of E°, the easier it is to reduce the species on the
left of the half-equation.
ii. The less positive the value of E°, the easier it is to oxidise the species on the
right of the half-equation.
CHAPTER 25: Transition Elements
25.1 Introduction to Transition Elements
25.2 Oxidation States of Transition Elements
25.3 Complex Ions

Learning outcomes:

(a) explain what is meant by a transition element, in terms of d-block elements forming one or
more stable ions with incomplete d orbitals.
(b) state the electronic configuration of a first row transition element and of its ions.
(c) contrast, qualitatively, the melting points and densities of the transition elements with those of
calcium as a typical s-block element.
(d) describe the tendency of transition elements to have variable oxidation states.
(e) predict from a given electronic configuration, the likely oxidation states of a transition element.
(f) describe and explain the use of Fe³⁺/Fe²⁺, MnO4⁻/Mn²⁺ and Cr2O7²⁻/Cr³⁺ as examples of
redox systems.
(g) predict, using E values, the likelihood of redox reactions.
(h) explain the reactions of transition elements with ligands to form complexes, including the
complexes of copper(II) ions with water, hydroxide, ammonia and chloride ions
(i) (i) define the term ligand as a species that contains a lone pair of electrons that forms a dative
bond to a central metal atom/ion.
(ii) define the term complex as a molecule or ion formed by a central metal atom/ion
surrounded by one or more ligands.
(iii) describe transition metal complexes as linear, octahedral, tetrahedral or square planar.
(j) explain qualitatively that ligand exchange may occur, including the complexes of copper(II)
ions with water, hydroxide, ammonia and chloride ions.
(k) describe the shape and symmetry of the d orbitals, and the splitting of degenerate d orbitals
into two energy levels in octahedral complexes using the complexes of copper(II) ions with
water and ammonia as examples.
(l) explain the origin of colour in transition element complexes resulting from the absorption of
light energy as an electron moves between two non-degenerate d orbitals.
(m) describe, in qualitative terms, the effects of different ligands on absorption, and hence colour,
using the complexes of copper(II) ions with water, hydroxide, ammonia and chloride ions as
examples.
(n) apply the above ideas of ligands and complexes to other metals, given information.
25.1 Introduction to Transition Elements
Transition and d-block elements

1) A transition element is one which forms one or more stable ions with incompletely
filled orbitals.

2) A d-block element is one which has electrons filling the d-orbitals.

3) From the above definition, scandium and zinc are not counted as transition
elements, although they are d-block elements. This is because:
i. scandium forms Sc³⁺ ion, which does not have any d-electrons.
ii. zinc forms Zn²⁺ ion, which has a completely-filled d-orbitals.
Physical properties of transition elements

1) i. Transition elements are all metals which are hard and denser than s-block
elements.
ii. This is because the relative atomic masses of transition elements are higher
and their radii are smaller compared to s-block elements. Hence, there are
more mass per unit volume and the density is higher.
iii. For example, iron has a density of 7.9 g cm⁻³ while calcium has a density of
1.6 g cm⁻³.

2) i. Transition elements have higher melting points than s-block elements.

ii. This is because the metallic bond of transition elements is stronger as both 3d
and 4s electrons are involved in the bonding. In calcium, for example, only 3s
electrons are involved.
iii. This is possible because 3d and 4s and very similar energy levels.
iv. For example, iron has a melting point of 1538 °C while calcium has a melting
point of 839 °C.

Characteristic properties of transition elements

1) The characteristic properties of transition elements are:

i. they have variable oxidation states.
ii. they form coloured ions.
iii. they form complex ions which are surrounded by ligands.
iv. they often act as catalysts.

25.2 Oxidation States of Transition Elements

Variable oxidation states

1) i. One characteristic property of transition elements is that they have variable

oxidation states.
ii. For example, iron can exist in 0, +2 or +3 oxidation state.

2) This is because the 4s and 3d electrons have very similar energy levels, therefore
the transition element can easily lose or gain electrons to form ions/compounds
of roughly the same stability.
3) All the possible oxidation states of the transition elements are shown below, the
most common ones are bolded.

4) An oxidation state of +2 implies that two electrons have been lost from the
neutral element. The same goes for other oxidation states.

5) The maximum oxidation state of a compound can be obtained by counting

the number of 4s electrons and the number of unpaired 3d electrons.
Only copper breaks this pattern.

6) i. For small oxidation states, the transition element normally exists as simple
Mª⁺ ions.
ii. For large oxidation states, the transition element normally exists in oxo-
compounds. This is because the ions formed would have a very high charge
density and it will polarise adjacent molecules(water, oxygen) to form the oxo-
compounds.
iii. For example, Cr⁶⁺ does not exist, chromium with oxidation state +6 exists as
CrO4²⁻.

Redox reactions of transition elements.

Note: 1) There is no point learning this here, you should already have a decent
knowledge on the Fe³⁺/Fe²⁺, MnO4⁻/Mn²⁺ and Cr2O7²⁻/Cr³⁺ systems up to
this point of the syllabus.
2) You need to know how to:
i. construct redox equations.
ii. calculate oxidation states.
iii. calculate the amount of substance(mass/volume) from a titration that
involves oxidation and reduction.
iv. select suitable oxidising and reducing agents.
v. calculate cell potentials.
25.3 Complex Ions
Ligand and complex

1) A ligand is a molecule or ion with a lone pair of electrons, capable of forming a

co-ordinate bond to a metal atom or ion. Some examples of ligands are water,
ammonia and chloride ion.

2) A complex is a molecule or ion containing a central metal ion surrounded by one

or more ligands. Some examples are [Al(H2O)6]³⁺ and [Fe(H2O)6]³⁺.

Formation of a complex

1) A complex is formed when ligands bond with the central metal ion via
co-ordinate bonding.

2) Take [Fe(H2O)6]³⁺ as an example:

i. Fe ion has an electronic structure of [Ar]3d⁶4s². When
it loses electrons to become Fe³⁺, the electronic
structure becomes [Ar]3d⁵.
ii. The ion then uses 6 orbitals from the 4s, 4p and 4d
levels to accept lone pairs from the water molecules.

3) Note: i. For small ligands such as water and ammonia, six is the maximum
number of ligands it can bond to the central metal ion.
ii. For larger ligands such as chloride ions, it can only form four co-
ordinate bonds with the central metal ion.
4) The co-ordination number of a complex is the total number of co-ordinate
bond the ligands formed with the central metal ion. For example,
[Fe(H2O)6]³⁺ has a co-ordination number of 6.

5) Some other co-ordination numbers and the geometry of the complex:

6) A ligand is said to be unidentate if it forms one co-ordinate bond with the

central metal ion only. Water, ammonia and chloride are unidentate ligands.

7) i. A ligand is said to be bidentate if it forms two co-ordinate bonds with the

central metal ion. 1,2-diaminoethane and ethandioate ion are bidentate
ligands.

ii. A complex ion which has bidentate ligands attached to it exhibits optical
isomerism.
 iii. In addition, a complex ion which has the ligands arranged in a square planar
structure exhibits geometrical isomerism.

Naming complexes

1) Naming complexes is very similar in naming organic compounds.

2) Each ligand is given a code:

3) Some examples:
i. [Fe(H2O)6]³⁺ is hexaaquairon(III) ion
- hexa shows there are six ligands.
- aqua shows the ligands are water molecules.
- iron shows the name of the central metal ion.
- (III) shows the the oxidation number of the central metal ion.

4) If there are more than one type of ligands, the ligands are named according to
alphabetical order, ignoring the prefixes. For example, [Cu(NH3)4(H2O)2]²⁺ is
called tetraamminediaquacopper(II) ion.

5) i. For cationic complex, the name of the central metal ion is the same as its ooo
original name.
ii. For anionic complex, the name of the central metal ion follows this coding:
 iii. For example, [CuCl4]²⁻ is called tetrachlorocuprate(II) ion. (It is yellow colour)

Ligand exchange

1) A ligand exchange reaction is a reaction in which one ligand in a complex

ion is replaced by a different one.

2) Example 1: Replacing water with chloride ions.

i. When concentrated hydrochloric acid is added to a solution containing
hexaaquacobalt(II) ions, the solution turns from pink to dark rich blue. The
six water molecules are replaced by four chloride ions.

ii. Only four chloride ions are attached because chloride ions are larger,
therefore six chloride ions cannot fit in around the central metal ion.
iii. The co-ordination number of the complex changes from 6 to 4. The
geometry of ligands around changes from octahedral to tetrahedral.
iv. By Le Chatelier's principle, the process can be reversed by adding water to it.

3) Example 2: Replacing water with ammonia.

i. The ammonia can act as a base and also a ligand. This is because
hexaaqua- ions are acidic.
ii. The acidity of hexaaqua- ions is due to the electron pair in the water
molecule being pulled towards the central positive charge, making the
hydrogen more positive, and easily lost.
 Stage 1: Ammonia as a base(Acid-base reaction)
iii. When small amount of ammonia is added, hydrogen ions from the water are
pulled out, leaving hydroxide ions.

iv. A precipitate will be formed when two hydrogen ions have been
removed. This is because a neutral complex is produced and it is
unattractive to water molecules. Hence, it is no longer soluble in water.
Stage 2: Ammonia as a ligand(ligand exchange reaction)
v. When excess ammonia is added, the precipitate dissolves. The ammonia
replaces water as a ligand to give tetraamminediaquacopper(II) ions. Notice
that only 4 of the 6 water molecules are replaced.

Overall reaction:

4) Certain ligands are stronger than other and central metal ions generally
prefer to be bonded to stronger ligands. Therefore a ligand exchange
reaction may not happen if the new ligand is weaker than the original ligand.
Colour of complexes

1) Visible light is the visible part of the electromagnetic spectrum which has
wavelengths between 400 nm to 700 nm.

2) White light is composed of all the wavelengths in the visible part of the
electromagnetic spectrum. When white light is passed through a prism, it splits
into its constituent colours. This phenomenon is known as dispersion of light.

3) When white light passes through copper(II) sulfate, CuSO4 solution, visible light
with wavelengths in the red and yellow region is absorbed. The unabsorbed
ones combine to given a pale blue(cyan) colour.

4) The colour we see is the complementary colour of the

wavelength(colour) of the light absorbed by the substances. The
complementary colour wheel can be used to estimate the colour of a
substance. Colours on opposite sites are complementary colours.
Shapes of d-orbitals

1) There are five types of d-orbitals, named dxy, dxz, dyz, dz² and dx²-y².

2) i. dxy, dxz and dyz have the 'lobes' in the x-y, x-z and y-z planes respectively. Note
that the 'lobes' does not touch the axes, they are located between the axes.

ii. dz² has the 'lobes' along the z-axis, with a 'collar'.

iii. dx²-y² has the 'lobes' along the x- and y-axes.

Factors affecting the colour of complexes

1) The colour of a complex ion depends on the wavelength(or frequency) of the

visible light absorbed. This in turn depends on the energy gap, ∆E between
the two groups of d-orbitals(see below).
2) For an octahedral complex:
i. The central metal ion has five degenerate d-orbitals. They split into two
groups, two with higher energy and the other three with lower when
ligands are attached to it.
ii. This is because as the lone pairs on the ligands approach the central metal
ion, the d-electrons in the central metal ion are repelled.
iii. Due to the shape of the octahedral complex, the d-electrons repelled are the
ones in the dz² and dx²-y² orbitals, and these orbitals will have higher energy.

3) Other shapes have the splitting as below(not required in A-levels).

4) The size of the energy gap, ∆E depends on:

i. the oxidation number of the central metal ion.
- In general, the higher the oxidation state of the central metal ion, the larger
the size of ∆E.
ii. the nature of ligands.
- In general, the splitting, ∆E is larger if the lone pair comes from a less
electronegative atom.
5) The origin of colour of complexes:
i. As the electromagnetic radiation(photons) with frequencies within the visible
region of the electromagnetic spectrum passes through the complex, some of
the photons are absorbed.
ii. The photon absorbed must have energy equal to the energy gap of the
two groups of d-orbitals, which is given by ∆E = hf.
iii. The absorbed energy is used to promote an electron from a lower
energy d-orbital to a higher energy one. This is called d-d transition.

iv. The colour of the complex is the result of the unabsorbed frequencies of light
combining. It can then be estimated using the complementary colour wheel.

6) The reason why different complexes have different colours is because they all
have different energy gap size, ∆E. The incoming photon must have
frequency exactly equal to ∆E/h to be absorbed and be used to promote an
electron. Different colours and wavelengths of light have different frequencies,
which is why they have different colours.

7) Non-transition metal complexes are often not coloured because they do not
have partly-filled d-electrons. Hence no photon is absorbed and no
electron is promoted.

8) Note: for non-physics students:

i. The higher the frequency, f of light(photon), the higher its energy, which is
given by ∆E = hf, where h is the Planck's constant.
ii. There is an inverse relationship between frequency, f and wavelength, λ, which
is given by c = fλ, where c is the speed of light.
iii. In the visible spectrum, red light has the lowest energy and violet the highest.
CHAPTER 26: Benzene and Its Compounds
26.1 Introduction to Aromatic Compounds
26.2 Reactions of Benzene and Alkylbenzene
26.3 Introduction to Phenols
26.4 Reactions of Phenols

Learning outcomes:

(a) describe the chemistry of arenes as exemplified by the following reactions of benzene and
methylbenzene:
(i) substitution reactions with chlorine and with bromine.
(ii) nitration.
(iii) complete oxidation of the side-chain to give a benzoic acid.
(iv) hydrogenation of the benzene ring to form a cyclohexane ring
(b) (i) describe the mechanism of electrophilic substitution in arenes, as exemplified by the
formation of nitrobenzene and bromobenzene.
(ii) suggest the mechanism of other electrophilic substitution reactions, given data.
(iii) describe the effect of the delocalisation of electrons in arenes in such reactions.
(c) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes
depending on reaction conditions.
(d) apply the knowledge of positions of substitution in the electrophilic substitution of arenes.
(e) recall the chemistry of phenol, as exemplified by the following reactions:
(i) with bases.
(ii) with sodium.
(iii) with diazonium salts.
(iv) nitration of, and bromination of, the aromatic ring
(f) describe and explain the relative acidities of water, phenol and ethanol.
(g) deduce the presence of a CH3CH(OH)– group in an alcohol from its reaction with alkaline
aqueous iodine to form tri-iodomethane.
(h) describe the reaction of CH3CO– compounds with alkaline aqueous iodine to give
tri-iodomethane.
26.1 Introduction to Aromatic Compounds
Aliphatic and aromatic compounds

1) i. Aliphatic compounds are organic compounds that have carbon atoms joined
together in straight chains, branched chains or non-aromatic rings.
ii. Aromatic compounds are organic compounds that contain one or more
benzene ring(in A-level). Examples of aromatic compounds:

The structure of benzene

1) Benzene is a hexagonal and planar molecule with the formula C6H6.

2) In benzene, each carbon atom undergoes sp² hybridisation

to give three hybrid orbitals and an unchanged p orbital
which is perpendicular to the plane containing the three
hybrid orbitals.

3) Two of the hybrid orbitals overlap with two other hybrid orbitals of carbon
atoms and the other overlaps with the orbital of hydrogen. The unchanged p
orbitals overlap with one another via a system of π bond to give a giant
molecular orbital. This orbital is above and below the plane containing the
carbon atoms.

4) The six electrons from each p orbital are then delocalised around the ring. A
delocalised electron does not belong to any carbon atom. This delocalisation of
electrons gives benzene a relatively stable structure.
5) In a benzene molecule, all the C-C bonds are identical, with a bond length
of 140 pm. This bond length is longer than a double bond but shorter than a
single bond. The bond angle between carbon atoms is 120º.

6) The stability of benzene is shown in its reluctance to undergo addition

reactions. This is because when electrons are added, the delocalisation will
be broken and so does the stability.

7) There are two common symbols for benzene, the right one is
generally preferred over the left one because it indicates that
the electrons are delocalised.

8) Before this modern structure was discovered, the Kekulé structure(right) was
used. However, the Kekulé structure could not account for the unexplained
properties of benzene.
i. The structure has three double bonds, so it should undergo addition
reactions like other alkenes do. However for real benzene, it does not
undergo addition reactions easily.
ii. Single and double bonds have different bond length, therefore Kekulé's
benzene should have a distorted hexagonal shape. However in real
benzene, all the C-C bonds are identical and it is a perfect hexagon.

Introduction to arenes

1) Arenes are aromatic hydrocarbons, that is, hydrocarbon that contains at least
one benzene ring.

2) Arenes have higher melting and boiling points than aliphatic

hydrocarbons.
i. This is because in aromatic hydrocarbons, temporary dipoles can be
easily set up between the delocalised electrons. Hence the van der Waals'
 forces are stronger.
ii. Benzenes with side chains also have permanent dipole forces between them.
This is because the presence of side chains makes them a polar molecule.

26.2 Reactions of Benzene and Alkylbenzene

Reactivity of benzene

1) Unlike alkenes, benzene is resistant to addition reactions. This is because it

involves breaking the delocalised electron system and thus losing its stability.

2) Instead, benzene undergoes substitution reactions. This involves replacing one

or more hydrogen atoms with another group of atoms.

3) Benzene is particularly attractive to electrophiles due to its high electron density.

Therefore benzene mainly undergoes electrophilic substitution.

4) The reactivity of benzene is also affected by the presence of other group(s) in

the benzene ring. This is known as substituent group effect, and it will be
explained later.

Electrophilic substitution

1) Electrophilic substitution is the replacement of an atom or a group of

atom by an electrophile. In benzene, the electrophile replaces the hydrogen
atom(s).

2) The general mechanism of electrophilic substitution:

i. Suppose, an electrophile X⁺ is generated from a compound XY. The
electrophile is attracted to the electron-rich region of the benzene ring.
ii. Two electrons from the delocalised electron system are used to form a
co-ordinate bond with the electrophile.

iii. An intermediate with the delocalised electron system partially broken is

formed.
 iv. Y⁻ ion, from XY has a lone pair of electrons on it and it forms a bond with the
hydrogen ion. The hydrogen loses its electrons to the delocalised electron
system to bond with Y⁻. The delocalised electron system is now
restored.

3) Summary of reactions that benzene and alkylbenzene undergoes:

i. Halogenation(addition of halogen) into the ring and side chain.
ii. Nitration(addition of nitro group, NO2).
iii. Oxidation of side chain.
iv. Hydrogenation.

Reaction of benzene - halogenation

1) Reagent : Chlorine/bromine gas, Cl2/Br2

Condition : Aluminium chloride, AlCl3 or iron(III) chloride, FeCl3
Product : Halobenzene

2) Benzene reacts with chlorine/bromine in the presence of halogen carriers

such as aluminium chloride, AlCl3 to form chloro- or bromobenzene,
respectively. One hydrogen atom in the benzene ring is substituted by the
halogen.

3) Use chlorine as an example of halogen:

C6H6 + Cl2 → C6H5Cl + HCl

4) The mechanism of this reaction - electrophilic substitution.

i. Aluminium chloride polarises the Cl-Cl bond to create the electrophile Cl⁺.
Cl2 + AlCl3 → Cl⁺ + AlCl4⁻
ii. The electrophile is attracted to the benzene, it then bonds with the benzene
using two electrons from the delocalised electron system. Note that the
delocalised electron system is partially broken in the intermediate.
 iii. A hydrogen ion is expelled from the ring by AlCl4⁻ and leaving its electrons in
the ring. The delocalised electron system is now restored. Steamy fumes of
hydrogen chloride is also observed.

Reaction of benzene - nitration

1) Reagent : Concentrated nitric acid, HNO3

Condition : Reflux at a temperature lower than 50 ºC and the
presence of concentrated sulfuric acid, H2SO4 as catalyst
Product : Nitrobenzene

2) Nitration happens when one or more hydrogen atoms in benzene is replaced by

a nitro group, NO2.

3) Benzene reacts with nitric acid in the presence of concentrated sulfuric acid to
give nitrobenzene.
C6H6 + HNO3 → C6H5NO2 + H2O

4) The mechanism of this reaction - electrophilic substitution.

i. The electrophile, nitronium ion, NO2⁺ is formed by the reaction of nitric acid
and sulfuric acid.
HNO3 + 2H2SO4 → NO2⁺ + 2HSO4⁻ + H3O⁺
ii. As before, the electrophile is attracted to the benzene ring and forms a bond
with it. The delocalised electron system is partially broken.

iii. Hydrogen ion is expelled and it bonds with HSO4⁻ to regenerate the catalyst.
The delocalised electron system is restored.
5) If the temperature exceeds 50 ºC, 1,3-dinitrobenzene will be formed as well.
Notice that the second nitro group is added to the 3 position of the ring.

Substituent group effect

1) If a benzene already has a first substituent in it, second incoming substituent is

affected by the nature of the first substituent.

2) The first substituent has an effect on:

i. the position of the incoming second substituent.
- If X is an electron-withdrawing group, it deactivates the ring
and it is 3-directing.
- Examples are -NO2, -CN, -COOH, -CHO and -COR.
- If X is an electron-donating group, it activates the ring and it is
2,4-directing.
- Examples are -OH, -NH2, -C6H5 and alkyl groups.
- The only exception are halogens, they are electron-withdrawing but
they are 2,4-directing.
ii. the rate at which the second substituent is introduced.
- If X is an electron-withdrawing group, it deactivates the ring and the
rate of reaction decreases
- If X is an electron-donating group, it activates the ring and the rate of
reaction increases.

Reaction of alkylbenzene - halogenation

1) Reagent : Chlorine/bromine gas, Cl2/Br2

Condition : Into the ring - Aluminium chloride, AlCl3 or iron(III)
chloride, FeCl3 as catalyst, absence of UV
light
Into the alkyl group - Absence of catalyst but presence of
UV light
Product : Halo-alkylbenzene

2) In the presence of halogen carriers and the absence of UV light at

room temperature, the halogen is substituted into the ring via electrophilic
substitution.
3) Take methylbenzene as an example, since methyl group is electron-donating
and 2,4-directing, the incoming halogen is substituted at the 2 or 4 position.
2-chloro and 4-chloromethylbenzene are produced.
C6H5CH3 + Cl2 → C6H4ClCH3 + HCl

4) In the presence of UV light and the absence of halogen carriers, the

halogen is substituted into the alkyl group via free-radical substitution. Take
methylbenzene as an example, (chloromethyl)benzene is produced.
C6H5CH3 + Cl2 → C6H4(CH3Cl) + HCl

5) Further substitutions are possible, producing (dichloromethyl)benzene and

(trichloromethyl)benzene.

Reaction of alkylbenzene - nitration

1) Reagent : Concentrated nitric acid, HNO3

Condition : Reflux at a temperature lower than 30 ºC and the
presence of concentrated sulfuric acid, H2SO4 as catalyst
Product : Nitro-alkylbenzene

2) Since methyl group activates the ring, making the ring more reactive, the
temperature has to be lowered to 30 ºC to prevent multiple substitutions.
3) Methyl group is an electron-donating group, it activates the ring and is
2,4-directing, therefore the nitro group is substituted at the 2 or 4 positions

4) Take methylbenzene as an example, 2-nitro and 4-nitromethylbenzene is

produced.

5) If the temperature exceeds 30 ºC, multiple substitutions by nitro groups is

possible. However, each time a nitro group substitutes, the rate of reaction of
the next substitution decreases because nitro group is electron-withdrawing.
Therefore, 2,4,6-trinitromethylbenzene is rare.

Reaction of alkylbenzene - oxidation

1) Reagent : Acidified potassium manganate(VII), KMnO4

Condition : Heat or reflux
Product : Benzoic acid

2) When methylbenzene is heated under reflux with acidified potassium

manganate(VII), side-chain oxidation occurs. Benzoic acid is produced.

3) Any carbon side-chain group is oxidised to -COOH group under these

conditions.
Reaction of alkylbenzene - hydrogenation

1) Reagent : Hydrogen gas, H2

Condition : Heat in the presence of nickel, Ni catalyst at 150 °C
Product : Cyclohexanes

2) In hydrogenation, hydrogen atoms are added to the benzene ring. The

delocalised electron system is permanently broken.

3) With benzene:

4) With methylbenzene:

26.3 Introduction to Phenols

What are phenols?

1) Phenols are benzene compounds which have an -OH group

attached directly to it.

2) In a phenol molecule, one of the lone pairs on the oxygen overlaps with
the delocalised electron system to give a structure like this:
3) This increases the electron density of the delocalised electron system. It
makes phenols much more reactive than benzene itself. Also, it increases
the acidity of phenol as well.

4) Physical properties of phenols:

i. Phenol has a higher melting and boiling points than methylbenzene.
- This is because phenols can form hydrogen bonds between them in
addition of van der Waals' forces and permanent dipole-dipole forces.

ii. Phenol itself is more soluble in water than other phenols.

- This is because a small phenol molecule can form more effective hydrogen
bonds with water molecules.
- However, most phenols are generally insoluble in water.

Acidity of phenols

1) Compounds like alcohols and phenols which contain an -OH group attached to
a hydrocarbon are very weak acids.

2) Alcohol's strength as an acid is so weak that it is ignored under normal

situations. However, phenols have recognisable acid strength.

3) This is because phenol can donate a proton to form a phenoxide ion. The
presence of hydroxonium ions makes it acidic.

Comparing the strength of organic acids

1) The strength of organic acids depends on:

i. The strength of the O-H bond which is to be broken.
ii. The stability of the anion formed.
2) The strengths of the acids are as follow. The lower the value of pKa, the stronger
the acid is.

3) Ethanoic acid is the strongest because of the stability of ethanoate ion formed.
In an ethanoate ion, the negative charge is spread throughout the -COO
group. This delocalisation of electron and negative charge stabilises it to a
greater extent. However, since oxygen atoms are the most electronegative, more
negative charge will still be concentrated here.

4) Phenol is a weaker acid. This is because electron delocalisation of the

phenoxide ion is not as great as in ethanoate ion. Although the delocalised ring
electrons are involved, the electrons are still heavily distorted towards
the one electronegative oxygen atom rather than two in the ethanoate ion
case.
5) i. If an electron-withdrawing group is attached to phenol, its acidity
increases. This is because the electron-withdrawing group can attract
electrons away from the oxygen, stabilising the phenoxide ion formed.
ii. If an electron-donating group is attached to phenol, its acidity
decreases. This is because the electron-donating group increases the
electron density in the benzene ring, intensifying the charge on oxygen atom.

6) Ethanol is the weakest acid among all. This is because the

ethoxide ion formed has no spreading of its negative
charge to other parts, all the negative charge is
concentrated on the oxygen atom. This makes it
very attractive to hydrogen ions and it can easily accept
one.

7) On the other hand, water is a stronger acid than ethanol but weaker
than phenol. This is because in ethoxide ion, the presence of an alkyl
group intensifies the negative charge on the oxygen atom. In a
hydroxide ion, no such thing happens.

26.4 Reactions of Phenols

Reaction with sodium metal, Na

1) Reagent : Sodium metal, Na

Condition : Room temperature
Product : Alkoxides and hydrogen gas

2) Like alcohols, phenol will react with a reactive metal such as sodium to give
sodium phenoxide and hydrogen gas.
2C6H5OH + 2Na → 2C6H5O⁻Na⁺ + H2

3) The observation is that the sodium sinks and bubbles of hydrogen gas is
produced. This reaction is more vigorous than the one with alcohol because
phenol is more acidic.
Reaction with sodium hydroxide, NaOH

1) Reagent : Sodium hydroxide, NaOH solution

Condition : Room temperature
Product : Alkoxides and water

2) Phenol is a strong enough acid to react with sodium hydroxide solution to give
sodium phenoxide and water.
C6H5OH + NaOH → C6H5O⁻Na⁺ + H2O

3) Since alcohols will not react with sodium hydroxide, this can be used as
a test to distinguish alcohols from phenols.

4) However, phenol will not react with sodium carbonate and sodium
hydrogencarbonate because it's not acidic enough to react with these.

Halogenation

1) Reagent : Chlorine gas/bromine water

Condition : Room temperature
Product : 2,4,6-trihalophenol

2) Phenol will react with halogens even without the presence of halogen
carriers. This proves that phenol is more reactive than benzene itself.

3) Take bromine as an example, 2,4,6-tribromophenol is produced.

4) The observations are:

i. The reddish-brown of bromine decolourises.
ii. A white precipitate is formed, this is 2,4,6-tribromophenol.
iii. Steamy fumes of hydrogen bromide is observed.
Nitration

1) Reagent : Nitric acid, HNO3

Condition : Room temperature
Product : Nitrophenols

2) Unlike benzenes, concentrated sulfuric acid is not needed for nitration to

occur. This proves that phenol is more reactive than benzene itself.

3) i. With dilute nitric acid, mono-substituion occurs. 2-nitrophenol and

4-nitrophenol is produced.

ii. With concentrated nitric acid, tri-substituion occurs. 2,4,6-trinitrophenol

is produced.

Tri-iodomethane(iodoform) test for alcohols

1) This is a test used to identify the presence of

CH3CH(OH)- group in an alcohol. The R can be a
hydrogen or an alkyl group.

2) i. Iodine solution is added to a small amount of an alcohol, followed by just

enough sodium hydroxide solution to remove the colour of the iodine.
ii. If the alcohol contains the CH3CH(OH)- group, then a pale yellow
precipitate of tri-iodomethane, CHI3 is produced.

3) i. Ethanol is the only primary alcohol to give the tri-iodomethane

(iodoform) reaction.
 ii. If R is a hydrocarbon group, then you have a secondary alcohol. Lots of
secondary alcohols give this reaction, but those that do all have a methyl
group attached to the carbon with the -OH group.
iii. No tertiary alcohols can contain this group because no tertiary alcohols
can have a hydrogen atom attached to the carbon with the -OH group. No
tertiary alcohols give the triiodomethane (iodoform) reaction.

4) The flow scheme is as such:

5) The overall equation is:

Tri-iodomethane(iodoform) test for carbonyl compounds

1) This is a test used to identify the presence of CH3CO-

group in carbonyl compounds. The R can be a hydrogen or
an alkyl group.

2) i. Iodine solution is added to a small amount of an alcohol, followed by just

enough sodium hydroxide solution to remove the colour of the iodine.
ii. If the alcohol contains the CH3CH(OH)- group, then a pale yellow
precipitate of tri-iodomethane, CHI3 is produced.
3) i. Ethanal is the only aldehyde to give the triiodomethane(iodoform)
reaction.
ii. If R is a hydrocarbon group, then you have a ketone. Lots of ketones give
this reaction, but those that do all have a methyl group on one side of the
C=O bond.

4) The overall equation is: