5.1.

1 Lattice Energy & Enthalpy Change of

Atomisation
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Lattice Energy & Enthalpy Change of Atomisation

 Enthalpy change (ΔH) refers to the amount of heat energy transferred during a

chemical reaction, at a constant pressure

Enthalpy change of atomisation

 The standard enthalpy change of atomisation (ΔHatꝋ) is the enthalpy change when 1

mole of gaseous atoms is formed from its element under standard conditions
o Standard conditions in this syllabus are a temperature of 298 K and a pressure of
101 kPa
 The ΔHatꝋ is always endothermic as energy is always required to break any bonds
between the atoms in the element, to break the element into its gaseous atoms
o Since this is always an endothermic process, the enthalpy change will always
have a positive value
 Equations can be written to show the standard enthalpy change of atomisation (ΔHatꝋ) for
elements
 For example, sodium in its elemental form is a solid
 The standard enthalpy change of atomisation for sodium is the energy required to form 1
mole of gaseous sodium atoms:

Na(s) → Na(g) ΔHatꝋ = +107 kJ mol -1

Worked example: Writing equations for the standard enthalpy change of

atomisation
Answer

Answer 1: Potassium in its elemental form is a solid, therefore the standard enthalpy change of
atomisation is the energy required to form 1 mole of K(g) from K(s)

K(s) → K(g) 

Answer 2: Mercury in its elemental form is a liquid, so the standard enthalpy change of
atomisation of mercury is the energy required to form 1 mole of Hg(g) from Hg(l)

Hg(l) → Hg(g)

Lattice energy

 The lattice energy (ΔHlattꝋ) is the enthalpy change when 1 mole of an ionic compound is

formed from its gaseous ions (under standard conditions)
 The ΔHlattꝋ is always exothermic, as when ions are combined to form an ionic solid
lattice there is an extremely large release of energy
o Since this is always an exothermic process, the enthalpy change will always have
a negative value
o Because of the huge release in energy when the gaseous ions combine, the value
will be a very large negative value
 The large negative value of ΔHlattꝋ suggests that the ionic compound is much
more stable than its gaseous ions
o This is due to the strong electrostatic forces of attraction between the
oppositely charged ions in the solid lattice
o Since there are no electrostatic forces of attraction between the ions in the gas
phase, the gaseous ions are less stable than the ions in the ionic lattice
 o The more exothermic the value is, the stronger the ionic bonds within the
lattice are
 The ΔHlattꝋ of an ionic compound cannot be determined directly by one single experiment
 Multiple experimental values and an energy cycle are used to find the ΔHlattꝋ of ionic
compounds
 The lattice energy (ΔHlattꝋ) of an ionic compound can be written as an equation
o For example, magnesium chloride is an ionic compound formed from magnesium
(Mg2+) and chloride (Cl-) ions
o Since the lattice energy is the enthalpy change when 1 mole of magnesium
chloride is formed from gaseous magnesium and chloride ions, the equation for
this process is:

Mg2+(g) + 2Cl-(g) → MgCl2(s)

Worked Example: Writing equations for lattice energy

Answer

Answer 1: Mg2+(g) + O2-(g) → MgO(s)

Answer 2: Li+(g) + Cl-(g) → LiCl(s)

Exam Tip
Make sure the correct state symbols are stated when writing these equations – it is crucial that
you use these correctly throughout this entire topic.
5.1.2 Electron Affinity & Trends of Group 16 &
17 Elements
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Electron Affinity
Electron affinity

 The first electron affinity (EA1) is the enthalpy change when 1 mole of electrons is

added to 1 mole of gaseous atoms, to form 1 mole of gaseous ions each with a
single negative charge under standard conditions

X(g) + e- → X-(g)

 EA1 is usually exothermic, as energy is released

o Since this is generally an exothermic process, then the value for EA1 will usually
be a negative number
 An element can also accept more than one electron, in which case successive electron
affinities are used
o For example, the second electron affinity (EA2) and third electron affinity (EA3)
of an element represent the formation of 1 mole of gaseous ions with 2- and 3-
charges respectively
 The second and third electron affinities are endothermic, as energy is absorbed
o This is because the incoming electron is added to an already negative ion
o Energy is required to overcome the repulsive forces between the incoming
electron and negative ion
o Since these are endothermic processes, the values will be positive

Second & third electron affinity table

Factors affecting electron affinity

 The value of the electron affinity depends on how strongly the incoming electron is
attracted to the nucleus
o The greater the attractive forces between the electron and nucleus, the more
energy is released and therefore the more exothermic (more negative)
the EA1 value will be
 The factors affecting the electron affinity of an element are the same as those that affect
the ionisation energy (the formation of positive ions via the loss of electrons)
 These are:
o Nuclear charge: the greater the nuclear charge, the stronger the attractive forces
between an incoming electron and the nucleus
o Distance: the greater the distance between the nucleus and the outermost
shell/orbital where the electron is added, the weaker the force of attraction
o Shielding: the greater the number of shells, the greater the shielding effect and the
weaker the force of attraction

Trends in electron affinity of Group 16 & Group 17 elements

 Electron affinities of non-metals become more exothermic across a period, with a

maximum at Group 17
  There is generally a downwards trend in the size of the electron affinities of the elements
in Group 16 and 17
o The electron affinities generally become less exothermic for each successive
element going down both Groups, apart from the first member of each Group
(oxygen and fluorine respectively)

Electron affinity table

 An atom of chlorine has a greater nuclear charge than an atom of sulfur

 Chlorine will therefore have a greater attractive force between its nucleus and its outer
electrons
o More energy is released upon adding an electron to chlorine, so the EA1 of Cl
is more exothermic than for S
  Going down Group 16 and 17:
o The outermost electrons are held less tightly to the nucleus as they are further
away
o The number of electron shells increases causing an increased shielding of the
outermost electrons
o It gets more difficult to add an electron to the outer shell
o Less energy is released upon adding an electron to the outer shell
o So generally, the EA1 becomes less exothermic
 Fluorine is an exception and has a lower EA1 than chlorine
o Fluorine has a very small atomic radius
o This means that the electron density of fluorine is high
o There is more repulsion between the incoming electron and the electrons that are
already present in fluorine
o These repulsive forces reduce the attractive forces between the incoming
electron and nucleus
o As a result, the EA1 of fluorine is less exothermic than expected

5.1.3 Constructing Born-Haber Cycles

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Constructing Born-Haber Cycles

 To calculate the lattice energy (ΔHlattꝋ) of an ionic compound, a Born-Haber cycle is

used, which is a special type of energy cycle
 To find the ΔHlattꝋ of an ionic compound, the following values must be known:
o Enthalpy change of formation (ΔHfꝋ)
o The various enthalpy changes involved when going from elements in
their standard states to their gaseous ions (the sum of all of these can be referred
to as ΔH1ꝋ)
 The various enthalpy changes involved when going from elements in their standard states
to their gaseous ions include:
o Enthalpy change of atomisation of each element
o First ionisation energy of the metal
o Successive ionisation energies of the metal if applicable
o First electron affinity of the non-metal
o Successive electron affinities of the non-metal if applicable
 The order that these are written in the Born-Haber cycle is important - they must be
done in the order written above
o First ionisation energy cannot take place before atomisation, because first
ionisation energy is the process of turning gaseous atoms into gaseous ions
 o Electron affinity cannot take place before first ionisation energy, since the
electrons must be lost from the metal first during ionisation, to be present in order
for the non-metal to gain them
 Hess’s law states that ‘the enthalpy change in a chemical reaction is the same regardless
of the route taken, as long as the final and initial conditions and states of reactants and
products are the same for each route’
 Although a Born-Haber cycle is usually constructed and used to calculate the lattice
energy of an ionic compound, the cycle could be used to calculate any stage in the cycle,
since an energy change is the same regardless of the route taken
 For example, the energy cycle shows that there are two routes to go from the elements in
their standard states to the ionic compound:
o Each route begins at the same stage of the cycle and ends at the same stage of the
cycle
 According to Hess’s law, the enthalpy change for both routes is the same, so the cycle
can be used to calculate an unknown value within the cycle

The green arrow shows the indirect route, which is equal in energy to the direct route of the
element in the standard states changing into the ionic compound (blue arrow)

Worked example: Constructing a Born-Haber cycle for KCl

Worked example: Constructing a Born-Haber cycle for MgO
Exam Tip
When constructing Born-Haber cycles, be sure to use ionisation energies  (IE) for metals (as
metals lose electrons) and electron affinities  (EA) for non-metals (as non-
metals gain electrons).Remember that the order that the steps go in is important!

5.1.4 Calculations using Born-Haber Cycles

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Calculations Using Born-Haber Cycles

 Once a Born-Haber cycle has been constructed, it is possible to calculate the lattice
energy (ΔHlattꝋ) by applying Hess’s law and rearranging:

ΔHfꝋ = ΔHatꝋ + ΔHatꝋ + IE + EA + ΔHlattꝋ

 If we simplify this into three terms, this makes the equation easier to see:
o ΔHlattꝋ
o ΔHfꝋ
o ΔH1ꝋ (the sum of all of the various enthalpy changes necessary to convert the
elements in their standard states to gaseous ions)
 The simplified equation becomes

ΔHfꝋ = ΔH1ꝋ + ΔHlattꝋ

So, if we rearrange to calculate the lattice energy, the equation becomes

ΔHlattꝋ = ΔHfꝋ - ΔH1ꝋ

 When calculating the ΔHlattꝋ, all other necessary values will be given in the question
 A Born-Haber cycle could be used to calculate any stage in the cycle
o For example, you could be given the lattice energy and asked to calculate the
enthalpy change of formation of the ionic compound
o The principle would be exactly the same
o Work out the direct and indirect route of the cycle (the stage that you are being
asked to calculate will always be the direct route)
o Write out the equation in terms of enthalpy changes and rearrange if necessary to
calculate the required value
 Remember: sometimes a value may need to be doubled or halved, depending on the
ionic solid involved
o For example, with MgCl2 the value for the first electron affinity of chlorine would
need to be doubled in the calculation, because there are two moles of chlorine
atoms
o Therefore, you are adding 2 moles of electrons to 2 moles of chlorine atoms, to
form 2 moles of Cl- ions
Worked example: Calculating the lattice energy of KCl

Answer

 Step 1: The corresponding Born-Haber cycle is:

 
  Step 2: Applying Hess’ law, the lattice energy of KCl is:

ΔHlattꝋ = ΔHfꝋ - ΔH1ꝋ

ΔHlattꝋ = ΔHfꝋ - [(ΔHatꝋ K) + (ΔHatꝋ Cl) + (IE1 K) + (EA1 Cl)]

 Step 3: Substitute in the numbers:

ΔHlattꝋ = (-437) - [(+90) + (+122) + (+418) + (-349)] = -718 kJ mol-1

Worked example: Calculating the lattice energy of MgO

Answer

 Step 1: The corresponding Born-Haber cycle is:

 
 Step 2: Applying Hess’ law, the lattice energy of MgO is:
 ΔHlattꝋ = ΔHfꝋ - ΔH1ꝋ

ΔHlattꝋ = ΔHfꝋ - [(ΔHatꝋ Mg) + (ΔHatꝋ O) + (IE1 Mg) + (IE2 Mg) + (EA1 O) + (EA2 O)]

 Step 3: Substitute in the numbers:

ΔHlattꝋ = (-602) - [(+148) + (+248) + (+736) + (+1450) + (-142) + (+770)]

= -3812 kJ mol-1

Exam Tip
Make sure you use brackets when carrying out calculations using Born-Haber cycles as you may
forget a +/- sign which will affect your final answer!

5.1.5 Factors Affecting Lattice Energy

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Lattice Energy: Ionic Charge & Radius

 The two key factors which affect lattice energy, ΔHlattꝋ, are the charge and radius of the
ions that make up the crystalline lattice

Ionic radius

 The lattice energy becomes less exothermic as the ionic radius of the ions increases

 This is because the charge on the ions is more spread out over the ion when the ions
are larger
 The ions are also further apart from each other in the lattice
o The attraction between ions is between the centres of the ions involved, so the
bigger the ions the bigger the distance between the centre of the ions
 Therefore, the electrostatic forces of attraction between the oppositely charged ions in
the lattice are weaker
 For example, the lattice energy of caesium fluoride (CsF) is less exothermic than the
lattice energy of potassium fluoride (KF)
o Since both compounds contain a fluoride (F-) ion, the difference in lattice energy
must be due to the caesium (Cs+) ion in CsF and potassium (K+) ion in KF
o Potassium is a Group 1 and Period 4 element
o Caesium is a Group 1 and Period 6 element
o This means that the Cs+ ion is larger than the K+ ion
o There are weaker electrostatic forces of attraction between the Cs+ and F- ions
compared to K+ and F- ions
o As a result, the lattice energy of CsF is less exothermic than that of KF
 The lattice energies get less exothermic as the ionic radius of the ions increases

Ionic charge

 The lattice energy gets more exothermic as the ionic charge of the ions increases

 The greater the ionic charge, the higher the charge density
 This results in stronger electrostatic attraction between the oppositely charged ions in
the lattice
 As a result, the lattice energy is more exothermic
 For example, the lattice energy of calcium oxide (CaO) is more exothermic than the
lattice energy of potassium chloride (KCl)
o Calcium oxide is an ionic compound which consists of calcium (Ca2+) and oxide
(O2-) ions
o Potassium chloride is formed from potassium (K+) and chloride (Cl-) ions
o The ions in calcium oxide have a greater ionic charge than the ions in potassium
chloride
o This means that the electrostatic forces of attraction are stronger between the
Ca2+ and O2- compared to the forces between K+ and Cl-
o Therefore, the lattice energy of calcium oxide is more exothermic, as more
energy is released upon its formation from its gaseous ions
o Ca2+ and O2- are also smaller ions than K+ and Cl-, so this also adds to the value for
the lattice energy being more exothermic

5.1.6 Enthalpies of Solution & Hydration

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Enthalpy Change of Hydration & Solution

Enthalpy change of solution

 The standard enthalpy change of solution (ΔHsolꝋ) is the enthalpy change when 1

mole of an ionic substance dissolves in sufficient water to form a very dilute solution
 The symbol (aq) is used to show that the solid is dissolved in sufficient water
o For example, the enthalpy changes of solution for potassium chloride are
described by the following equations:

KCl(s) + aq → KCl(aq)

OR

KCl(s) + aq → K+(aq) + Cl-(aq)

 ΔHsolꝋ can be exothermic (negative) or endothermic (positive)

Enthalpy change of hydration

 The lattice energy (ΔHlattꝋ) of KCl is -711 kJ mol-1

o This means that 711 kJ mol-1 is released when the KCl ionic lattice is formed
o Therefore, to break the attractive forces between the K+ and Cl- ions, +711 kJ mol-
1
 is needed
 However, the ΔHsolꝋ of KCl is +26 kJ mol-1
 This means that another +685 kJ mol-1 (711 - 26) is required to break the KCl lattice
 This is compensated for by the standard enthalpy change of hydration (ΔHhydꝋ)
 The standard enthalpy change of hydration (ΔHhydꝋ) is the enthalpy change when 1
mole of a specified gaseous ion dissolves in sufficient water to form a very
dilute solution
o For example, the enthalpy change of hydration for magnesium ions is described
by the following equation:

Mg2+(g) + aq → Mg2+(aq)


o Hydration enthalpies are the measure of the energy that is released when there is
an attraction formed between the ions and water molecules
o Hydration enthalpies are exothermic
 When an ionic solid dissolves in water, positive and negative ions are formed
 Water is a polar molecule with a δ- oxygen (O) atom and δ+ hydrogen (H) atoms which
will form ion-dipole attractions with the ions present in the solution
 The oxygen atom in water will be attracted to the positive ions and the hydrogen atoms
will be attracted to the negative ions
 Since the ΔHhydꝋ of KCl is -685 kJ mol-1, 685 kJ mol-1 is released in forming these ion-
dipole attractions when KCl dissolves in water
o This compensates for the remaining +685 kJ mol-1 which was needed to break
down the KCl lattice
The polar water molecules will form ion-dipole bonds with the ions in solution (a) causing the
ions to become hydrated (b)
5.1.7 Constructing Energy Cycles using
Enthalpy Changes & Lattice Energy
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Energy Cycle Using Enthalpy Changes & Lattice Energy

 The standard enthalpy change of hydration (ΔHhydꝋ) can be calculated by

constructing energy cycles and applying Hess’s law
Energy cycle involving enthalpy change of solution, lattice energy, and enthalpy change of
hydration
  The energy cycle shows that there are two routes to go from the ionic lattice to the
hydrated ions in an aqueous solution:
o Route 1: going from ionic solid → ions in aqueous solution (this is the direct
route)

ΔHsolꝋ= Enthalpy of solution

 Route 2: going from ionic lattice →  gaseous ions  →  ions in aqueous solution (this is
the indirect route)

-ΔHlattꝋ + ΔHhydꝋ = reverse lattice enthalpy + hydration enthalpies

Lattice enthalpy usually means Lattice formation enthalpy, in other words bond forming. If we

are breaking the lattice then this is reversing the enthalpy change so a negative sign is added in
front of the term (alternatively it is called lattice dissociation enthalpy)

 According to Hess’s law, the enthalpy change for both routes is the same, such that:

ΔHsolꝋ = -ΔHlattꝋ + ΔHhydꝋ

ΔHhydꝋ = ΔHsolꝋ + ΔHlattꝋ 

 Each ion will have its own enthalpy change of hydration, ΔHhydꝋ, which will need to be
taken into account during calculations
o The total ΔHhydꝋ is found by adding the  ΔHhydꝋ values of both anions and cations
together

Worked example: Constructing an energy cycle and energy level

diagram of KCl

Answer

Energy cycle:
Energy level diagram:
Worked example: Constructing an energy cycle and energy level
diagram of MgCl2

Answer

Energy cycle:
Energy level diagram:
5.1.8 Energy Cycle Calculations
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Energy Cycle Calculations

  The energy cycle involving the enthalpy change of solution (ΔHsolꝋ ), lattice energy
(ΔHlattꝋ), and enthalpy change of hydration (ΔHhydꝋ) can be used to calculate the different
enthalpy values
 According to Hess’s law, the enthalpy change of the direct and of the indirect route will
be the same, such that:

ΔHhydꝋ = ΔHlattꝋ + ΔHsolꝋ

 This equation can be rearranged depending on which enthalpy value needs to be

calculated
 For example, ΔHlattꝋ can be calculated using:

 ΔHlattꝋ = ΔHhydꝋ - ΔHsolꝋ

 Remember: the total ΔHhydꝋ is found by adding the ΔHhydꝋ values of both anions and
cations together
 Remember: take into account the number of each ion when completing calculations
o For example, MgCl2 has two chloride ions, so when completing calculations this
will need to be accounted for
o In this case, you would need to double the value of the hydration enthalpy, since
you are hydrating 2 moles of chloride ions instead of 1

Worked example: Calculating the enthalpy change of hydration of

chloride

Answer
Step 1: Draw the energy cycle of KCl

 
 Step 2: Apply Hess’s law  to find ΔHhydꝋ [Cl-]
 ΔHhydꝋ = (ΔHlattꝋ[KCl]) + (ΔHsolꝋ[KCl])

(ΔHhydꝋ[K+]) + (ΔHhydꝋ[Cl-])   =  (ΔHlattꝋ[KCl]) + (ΔHsolꝋ[KCl])

(ΔHhydꝋ[Cl-])   = (ΔHlattꝋ[KCl]) + (ΔHsolꝋ[KCl]) - (ΔHhydꝋ[K+])

 Step 3: Substitute the values to find ΔHhydꝋ [Cl-]

ΔHhydꝋ [Cl-]   = (-711) + (+26) - (-322) = -363 kJ mol-1

Worked example: Calculating the enthalpy change of hydration of

magnesium

Answer

 Step 1: Draw the energy cycle of MgCl2

 
 Step 2: Apply Hess’s law  to find ΔHhydꝋ [Mg2+]
 ΔHhydꝋ = (ΔHlattꝋ[MgCl2]) + (ΔHsolꝋ [MgCl2])

(ΔHhydꝋ[Mg2+]) + (2ΔHhydꝋ [Cl-])   = (ΔHlattꝋ [MgCl2]) + (ΔHsolꝋ [MgCl2])

(ΔHhydꝋ[Mg2+])   = (ΔHlattꝋ[MgCl2]) + (ΔHsolꝋ[MgCl2]) - (2ΔHhydꝋ[Cl-])

 Step 3: Substitute the values to find ΔHhydꝋ [Mg2+]

ΔHhydꝋ[Mg2+]  = (-2592) + (-55) - (2 x -363) = -1921 kJ mol-1

5.1.9 Factors Affecting Enthalpy of Hydration

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Enthalpy of Hydration: Ionic Charge & Radius

 The standard enthalpy change of hydration (ΔHhydꝋ) is affected by the amount that the ions
are attracted to the water molecules
 The factors which affect this attraction are the ionic charge and radius

Ionic radius

 ΔHhydꝋ becomes more exothermic with decreasing ionic radii

o Smaller ions have a greater charge density resulting in stronger ion-dipole
attractions between the water molecules and the ions in the solution
o Therefore, more energy is released when they become hydrated and
ΔHhydꝋ becomes more exothermic
 For example, the ΔHhydꝋ of magnesium sulfate (MgSO4) is more exothermic than the
ΔHhydꝋ of barium sulfate (BaSO4)
o Since both compounds contain a sulfate (SO42-) ion, the difference in ΔHhydꝋ must
be due to the magnesium (Mg2+) ion in MgSO4 and barium (Ba2+) ion in BaSO4
o Magnesium is a Group 2 and Period 3 element
o Barium is a Group 2 and Period 6 element
o This means that the Mg2+ ion is smaller than the Ba2+ ion
o The attraction is therefore much stronger for the Mg2+ ion
o As a result, the standard enthalpy of hydration of MgSO4 is more
exothermic than that of BaSO4

Ionic charge

 ΔHhydꝋ is more exothermic for ions with larger ionic charges

 o Ions with large ionic charges have a greater charge density resulting
in stronger ion-dipole attractions between the water molecules and the ions in the
solution
o Therefore, more energy is released when they become hydrated and
ΔHhydꝋ becomes more exothermic
 For example, the ΔHhydꝋ of calcium oxide (CaO) is more exothermic than the ΔHhydꝋ of
potassium chloride (KCl)
o Calcium oxide is an ionic compound that consists of calcium (Ca2+) and oxide (O2-)
ions
o Potassium chloride is formed from potassium (K+) and chloride (Cl-) ions
o Both of the ions in calcium oxide have a greater ionic charge than the ions in
potassium chloride
o This means that the attractions are stronger between the water molecules and
Ca2+ and O2- ions upon hydration of CaO
o The attractions are weaker between the water molecules and K+ and Cl- ions upon
hydration of KCl
o Therefore, the ΔHhydꝋ of calcium oxide is more exothermic as more energy is
released upon its hydration

The enthalpy of hydration is more exothermic for smaller ions and for ions with a greater
ionic charge
5.2.1 Entropy & Entropy Change
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Defining Entropy

 The entropy (S) of a given system is the number of possible arrangements of the

particles and their energy in a given system
o In other words, it is a measure of how disordered a system is
 When a system becomes more disordered, its entropy will increase
 An increase in entropy means that the system becomes energetically more stable
 For example, during the thermal decomposition of calcium carbonate (CaCO3) the
entropy of the system increases:

CaCO3(s) → CaO(s) + CO2(g)

 In this decomposition reaction, a gas molecule (CO2) is formed

 The CO2 gas molecule is more disordered than the solid reactant (CaCO3), as it is
constantly moving around
 As a result, the system has become more disordered and there is an increase in entropy

 Another typical example of a system that becomes more disordered is when a solid
is melted
 For example, melting ice to form liquid water:

H2O(s) → H2O(l)

 The water molecules in ice are in fixed positions and can only vibrate about those
positions
 In the liquid state, the particles are still quite close together but are arranged more
randomly, in that they can move around each other
 Water molecules in the liquid state are therefore more disordered
 Thus, for a given substance, the entropy increases when its solid form melts into a liquid
 In both examples, the system with the higher entropy will
be energetically the most stable (as the energy of the system is more spread out when it
is in a disordered state)
 Melting a solid will cause the particles to become more disordered resulting in a more
energetically stable system

Exam Tip
Make sure you don’t confuse the system with your surroundings!The system consists of the
molecules that are reacting in a chemical reaction.The surroundings are everything else such as
the solvent, the air around the reaction, test-tube, etc.

Entropy Changes

 All elements have positive standard molar entropy values

 The order of entropy for the different states of matter are as follows:

gas > liquid > solid

 
o There are some exceptions such as calcium carbonate (solid) which has a higher
entropy than mercury (liquid)
 Simpler substances with fewer atoms have lower entropy values than complex
substances with more atoms
o For example, calcium oxide (CaO) has a smaller entropy than calcium carbonate
(CaCO3)
 Harder substances have lower entropy than softer substances of the same type
o For example, diamond has a smaller entropy than graphite

Change in state

 The entropy of a substance changes during a change in state

 The entropy increases when a substance melts (change from solid to liquid)
o Increasing the temperature of a solid causes the particles to vibrate more
o The regularly arranged lattice of particles changes into an irregular arrangement
of particles
o These particles are still close to each other but can now rotate and slide over each
other in the liquid
o As a result, there is an increase in disorder
 The entropy increases when a substance boils (change from liquid to gas)
o The particles in a gas can now freely move around and are far apart from each
other
o The entropy increases significantly as the particles become very disordered
 Similarly, the entropy decreases when a substance condenses (change
from gas to liquid) or freezes (change from liquid to solid)
o The particles are brought together and get arranged in a more regular arrangement
o The ability of the particles to move decreases as the particles become more
ordered
o There are fewer ways of arranging the energy so the entropy decreases
The entropy of a substance increases when the temperature is raised as particles become more
disordered
  The entropy also increases when a solid is dissolved in a solvent
 The solid particles are more ordered in the solid lattice as they can only slightly vibrate
 When dissolved to form a dilute solution, the entropy increases as:
o The particles are more spread out
o There is an increase in the number of ways of arranging the energy
 The crystallisation of a salt from a solution is associated with a decrease in entropy
o The particles are spread out in solution but become more ordered in the solid

When a solid is dissolved in a solvent to form a dilute solution, the entropy increases as the
particles become more disordered

Entropy changes in reactions

 Gases have higher entropy values than solids

 So, if the number of gaseous molecules in a reaction changes, there will also be a change
in entropy
  The greater the number of gas molecules, the greater the number of ways of arranging
them, and thus the greater the entropy
 For example the decomposition of calcium carbonate (CaCO3)

 CaCO3(s) → CaO(s) + CO2(g)


o The CO2 gas molecule is more disordered than the solid reactant (CaCO3) as it can
freely move around whereas the particles in CaCO3 are in fixed positions in which
they can only slightly vibrate
o The system has therefore become more disordered and there is
an increase in entropy
 Similarly, a decrease in the number of gas molecules results in a decrease in entropy
causing the system to become less energetically stable

 For example, the formation of ammonia in the Haber process

N2(g) + 3H2(g) ⇋ 2NH3(g)


o In this case, all of the reactants and products are gases
o Before the reaction occurs, there are four gas molecules (1 nitrogen and 3
hydrogen molecules) in the reactants
o After the reaction has taken place, there are now only two gas molecules (2
ammonia molecules) in the products
o Since there are fewer molecules of gas in the products, there are fewer ways of
arranging the energy of the system over the products
o The system has become more ordered causing a decrease in entropy
o The reactants (N2 and H2) are energetically more stable than the product (NH3)

5.2.2 Calculating Entropy Changes

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Calculating Entropy Changes

 The standard entropy change (ΔSsystemꝋ ) for a given reaction can be calculated using the
standard entropies (Sꝋ ) of the reactants and products
 The equation to calculate the standard entropy change of a system is:

ΔSsystemꝋ = ΣΔSproductsꝋ - ΣΔSreactantsꝋ

(where Σ = sum of)

  For example, the standard entropy change for the formation of ammonia (NH3) from
nitrogen (N2) and hydrogen (H2) can be calculated using this equation

            N2(g) + 3H2(g) ⇋ 2NH3(g)

ΔSsystemꝋ = (2 x ΔSꝋ(NH3)) - (ΔSꝋ(N2) + 3 x ΔSꝋ(H2))

Worked example: Calculating entropy changes

Answer

ΔSsystemꝋ = ΣΔSproductsꝋ - ΣΔSreactantsꝋ

ΔSsystemꝋ = (2 x 38.20) - (2 x 32.60 + 205.0)

= -193.8 J K-1 mol-1

Exam Tip
Use the stoichiometry  of the equation and the correct state of the compounds when calculating
the entropy change of a reaction.
5.2.3 Gibbs Free Energy Change & Gibbs
Equation
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The Gibbs Equation

Gibbs free energy

 The feasibility of a reaction does not only depend on the entropy change of the reaction,
but can also be affected by the enthalpy change
 Therefore, using the entropy change of a reaction only to determine the feasibility of a
reaction is inaccurate
 The Gibbs free energy (G) is the energy change that takes into
account both the entropy change of a reaction and the enthalpy change
 The Gibbs equation is:

ΔGꝋ = ΔHreactionꝋ - TΔSsystemꝋ

 The units of ΔGꝋ are in kJ mol-1

 The units of ΔHreactionꝋ are in kJ mol-1
 The units of T are in K
 The units of ΔSsystemꝋ are in J K-1 mol-1 (and must therefore be converted to kJ K-1 mol-1 by
dividing by 1000)

The Gibbs Equation: Calculations

 The Gibbs equation can be used to calculate the Gibbs free energy change of a reaction

ΔGꝋ = ΔHreactionꝋ -  TΔSsystemꝋ

 The equation can also be rearranged to find values of ΔHreactionꝋ, ΔSsystemꝋ or the temperature,
T
 For example, if for a given reaction, the values of ΔGꝋ, ΔHreactionꝋ and ΔSsystemꝋ are given, the
temperature can be found by rearranging the Gibbs equation as follows:
Worked example: Calculating Gibbs free energy

Answer

 Step 1 - Calculate ΔSsystemꝋ

ΔSsystemꝋ = ΣΔSproductsꝋ - ΣΔSreactantsꝋ

ΔSsystemꝋ = (ΔSꝋ [CH3Br(g)] + ΔSꝋ [H2O(l)]) -  (ΔSꝋ [CH3OH(l)] + ΔSꝋ [HBr(g)])

= (246 + 70.0) - (240 + 99.0)

= -23.0 J K-1 mol-1
  Step 2 - Convert ΔSꝋ into kJ K-1 mol-1

= -0.023 kJ K-1 mol-1

  Step 3 - Calculate ΔGꝋ

ΔGꝋ = ΔHreactionꝋ - TΔSsystemꝋ

= -47 - (298 x -0.023)

= -40.146 kJ mol-1

= -40.1 kJ mol-1

5.2.4 Reaction Feasibility

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The Gibbs Equation: Reaction Feasibility

 The Gibbs equation can be used to calculate whether a reaction is feasible or not

ΔGꝋ = ΔHreactionꝋ - TΔSsystemꝋ

 When ΔGꝋ is negative, the reaction is feasible and likely to occur

 When ΔGꝋis positive, the reaction is not feasible and unlikely to occur

Worked Example
Worked example: Determining the feasibility of a reaction
Answer

 Step 1: Calculate ΔSsystemꝋ

ΔSsystemꝋ = ΣΔSproductsꝋ - ΣΔSreactantsꝋ

ΔSsystemꝋ = (2 x ΔSꝋ [CaO(s)]) -  (2 x ΔSꝋ [Ca(s)] + ΔSꝋ [O2(g)])

= (2 x 40.00) - (2 x 41.00 + 205.0)

= -207.0 J K-1 mol-1

 Step 2: Convert ΔSꝋ to kJ K-1 mol-1

= -0.207

 Step 3: Calculate ΔGꝋ

ΔGꝋ = ΔHreactionꝋ - TΔSsystemꝋ

= -635.5 - (298 x -0.207)

 = -573.8 kJ mol-1

 Step 4: Determine whether the reaction is feasible

Since the ΔGꝋ is negative the reaction is feasible and likely to occur

5.2.5 Reaction Feasibility: Temperature

Changes
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Feasibility & Temperature Changes

 The feasibility of a reaction can be affected by the temperature

 The Gibbs equation will be used to explain what will affect the feasibility of a reaction
for exothermic and endothermic reactions

Exothermic reactions

 In exothermic reactions, ΔHreactionꝋ is negative

 If the ΔSsystemꝋ is positive:
o Both the first and second term will be negative
o Resulting in a negative ΔGꝋ so the reaction is feasible
o Therefore, regardless of the temperature, an exothermic reaction with a positive
ΔSsystemꝋ will always be feasible
 If the ΔSsystemꝋ is negative:
o The first term is negative and the second term is positive
o At high temperatures, the -TΔSsystemꝋ will be very large and positive and will
overcome ΔHreactionꝋ
o Therefore, at high temperatures ΔGꝋ is positive and the reaction is not feasible
o The reaction is more feasible at low temperatures, as the second term will not be
large enough to overcome ΔHreactionꝋ resulting in a negative ΔGꝋ
 This corresponds to Le Chatelier’s principle which states that for exothermic
reactions an increase in temperature will cause the equilibrium to shift position in favour
of the reactants, i.e. in the endothermic direction
o In other words, for exothermic reactions, the products will not be formed at high
temperatures
o The reaction is not feasible at high temperatures
The diagram shows under which conditions exothermic reactions are feasible
Endothermic reactions

 In endothermic reactions, ΔHreactionꝋ is positive

 If the ΔSsystemꝋ is negative:
o Both the first and second term will be positive
o Resulting in a positive ΔGꝋ so the reaction is not feasible
o Therefore, regardless of the temperature, endothermic with a negative
ΔSsystemꝋ will never be feasible
 If the ΔSsystemꝋ is positive:
o The first term is positive and the second term is negative
o At low temperatures, the -TΔSsystemꝋ will be small and negative and will not
overcome the larger ΔHreactionꝋ
o Therefore, at low temperatures ΔGꝋ is positive and the reaction is less feasible
o The reaction is more feasible at high temperatures as the second term will
become negative enough to overcome the ΔHreactionꝋ resulting in a negative ΔGꝋ
 This again corresponds to Le Chatelier’s principle which states that for endothermic
reactions an increase in temperature will cause the equilibrium to shift position in favour
of the products
o In other words, for endothermic reactions, the products will be formed at high
temperatures
o The reaction is therefore feasible
The diagram shows under which conditions endothermic reactions are feasible
5.3.1 Electrolysis
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Products of Electrolysis

 Electrolysis is the breaking down of a compound into its elements using an electric
current
 For example, the electrolysis of zinc chloride (ZnCl2) into its elements zinc and chlorine

ZnCl2(s) → Zn(s) + Cl2(g)

 This method is often used to:

o Extract metals from their metal ores when the metals cannot be extracted by
heating their ores with carbon
o Purify metals
o Produce non-metals such as fluorine
 Electrolysis is carried out in an electrolysis cell which consists of:
o An electrolyte - this is the compound that is broken down during electrolysis and
it is either a molten ionic compound or a concentrated aqueous solution of ions
o Two electrodes - these are metal or graphite rods conduct electricity to the
electrolyte and away from the electrolyte
 The positive electrode is called the anode
 The negative electrode is called the cathode
o The power supply, which is direct current
 Electrolysis takes place in an electrochemical cell;

this type of electrochemical cell is called an electrolytic cell

Electrolysis of molten electrolytes

 Cations (positively charged ions) move to the negatively charged cathode where

they gain electrons
o Reduction takes place at the cathode
o If a metal is formed, a layer of metal is deposited on a cathode or it forms
a molten layer in the cell
 o If hydrogen gas is formed, bubbles are seen
o For example, silver and hydrogen both form positively charged ions which would
be reduced at the cathode as follows:

Ag+ + e- → Ag

2H+ + 2e- → H2

 Anions (negatively charged ions) move to the positively charged anode where they lose

electrons
o Oxidation takes place at the anode
o For example, bromine forms negatively charged ions which would be oxidised at
the anode as follows:

2Br- → Br2 + 2e-

Products formed by electrolysis when a pure molten ionic compound containing two simple
ions is electrolysed table
Electrolysis of aqueous solutions

 Aqueous solutions have more than one cation and anion in solution due to the presence
of water
 Water contributes H+ and OH- ions to the solution, which makes things more complicated
o Water is a weak electrolyte and splits into H+ and OH- ions as follows:

H2O ⇌ H+ + OH-

 The actual ions that are discharged during electrolysis will depend on:

o The relative electrode potential of the ions
o The concentration of the ions

Relative electrode potential of ions

 The relative electrode potential (Eꝋ) of ions describes how easily an ion is discharged

during electrolysis
 The positively charged cation with the most positive Eꝋ will be discharged at
the cathode as this is the cation that is most easily reduced
o For example, a concentrated aqueous solution of NaF will contain hydrogen (H+)
and sodium (Na+) ions
o The half-equations for the reduction of these ions and their Eꝋ values are as
follows:

2H+(aq) + 2e-  ⇌ H2(g)     Eꝋ =  0.00 V

Na+(aq) + e-  ⇌ Na(s)     Eꝋ = -2.71 V

 Since H+ ions have a higher Eꝋ value, hydrogen gas (H2) is formed at the cathode instead

of sodium (Na)
 The negatively charged anion with the most negative Eꝋ will be discharged at
the anode, as this is the anion that is most easily oxidised
o For example, a concentrated aqueous solution of NaF will contain hydroxide
(OH-) and fluoride (F-) ions
o The half-equations for the oxidation of these ions and their Eꝋ values are as
follows:

4OH-(aq)  → O2(g) + 2H2O(l) + 4e-        Eꝋ = -0.40 V

2F-(aq)  → F2(g) + 2e-        Eꝋ = -2.87 V

 Since F- ions have a lower Eꝋ value than OH- ions, fluorine (F2) gas is formed at the anode

Concentration of ions

 Ions that are present in higher concentrations are more likely to be discharged

  For example, when a concentrated solution of NaF is electrolysed, there are far
more fluoride ions which are discharged at the anode, instead of the hydroxide ions as
the fluoride ions are in higher concentration
o So, mainly fluorine will form at the electrode
 However, if a very dilute solution of NaF is electrolysed, there will be much
more oxygen and much less fluorine gas formed at the anode
o In reality, a mixture of both oxygen and fluorine gas is formed

Exam Tip
Electrolysis is a redox reaction as a reduction reaction takes place at one electrode and an
oxidation reaction at the other electrode.When writing the overall redox equation make sure that
the electrons lost at the anode balance the electrons gained at the cathode.

 Cathode: Cu2+ + 2e- → Cu

 Anode: 2Cl- → Cl2 + 2e-
 Overall: CuCl2 → Cu + Cl2

5.3.2 Faraday's Law & Avogadro

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Faraday's Law

 The amount of substance that is formed at an electrode during electrolysis is

proportional to:
o The amount of time where a constant current to passes
o The amount of electricity, in coulombs, that passes through the electrolyte
(strength of electric current)
o The relationship between the current and time is:

Q=Ixt

Q = charge (coulombs, C)

I = current (amperes, A)

t = time, (seconds, s)

 The amount or the quantity of electricity can also be expressed by the faraday (F) unit

o One faraday is the amount of electric charge carried by 1 mole of electrons or 1
mole of singly charged ions
o 1 faraday is 96 500 C mol-1
 Thus, the relationship between the Faraday constant and the Avogadro constant (L) is:
F=Lxe

F = Faraday’s constant (96 500 C mol-1)

L = Avogadro’s constant (6.022 x 1023 mol-1)

e = charge on an electron

Worked example: Determining the amount of electricity required

Answer

One Faraday is the amount of charge (96 500 C) carried by 1 mole of electrons

Answer 1
As there is one mole of electrons, one faraday of electricity (96 500 C) is needed to deposit one
mole of sodium.

Answer 2

Now, there are two moles of electrons, therefore, two faradays of electricity (2 x 96 500 C) are
required to deposit one mole of magnesium.

Answer 3

Two moles of electrons are released, so it requires two faradays of electricity (2 x 96 500 C) to

form one mole of fluorine gas.

Answer 4

Four moles of electrons are released, therefore it requires four faradays of electricity (4 x 96

500 C) to form one mole of oxygen gas.

Determining Avogadro's Constant by Electrolysis

 The Avogadro’s constant (L) is the number of entities in one mole

o L = 6.02 x 1023 mol-1
o For example, four moles of water contains 2.41 x 1024 (6.02 x 1023 x 4) molecules
of H2O
 The value of L (6.02 x 1023 mol-1) can be experimentally determined by electrolysis using
the following equation:

Finding L experimentally

 The charge on one mole of electrons is found by using a simple electrolysis experiment

using copper electrodes
Apparatus set-up for finding the value of L experimentally
  Method
o The pure copper anode and pure copper cathode are weighed
o A variable resistor is kept at a constant current of about 0.17 A
o An electric current is then passed through for a certain time interval (e.g. 40
minutes)
o The anode and cathode are then removed, washed with distilled water, dried with
propanone, and then reweighed
 Results
o The cathode has increased in mass as copper is deposited
o The anode has decreased in mass as the copper goes into solution as copper ions
o Often, it is the decreased mass of the anode which is used in the calculation, as the
solid copper formed at the cathode does not always stick to the cathode properly
o Let’s say the amount of copper deposited in this experiment was 0.13 g
 Calculation:
o The amount of charge passed can be calculated as follows:

Q=Ixt

= 0.17 x (60 x 40)

= 408 C

 To deposit 0.13 g of copper (2.0 x 10-3 mol), 408 C of electricity was needed

 The amount of electricity needed to deposit 1 mole of copper can therefore be calculated
using simple proportion using the relative atomic mass of Cu

Calculating the amount of charge required to deposit one mole of copper table
 Therefore, 199 292 C of electricity is needed to deposit 1 mole of Cu
 The half-equation shows that 2 mol of electrons are needed to deposit one mol of copper:

Cu2+(aq) +  2e- →   Cu(s)

 So, the charge on 1 mol of electrons is:

= 99 646 C

 Given that the charge on one electron is 1.60 x 10-19 C, then L equals:

 = 6.23 x 1023 mol-1

 The experimentally determined value for L of 6.23 x 1023 mol-1 is very close to

the theoretical value of 6.02 x 1023 mol-1

5.3.3 Standard Electrode & Cell Potentials

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Standard Electrode & Standard Cell Potentials

Electrode potential

 The electrode (reduction) potential (E) is a value which shows how easily a substance

is reduced
 These are demonstrated using reversible half equations
o This is because there is a redox equilibrium between two related species that are
in different oxidation states
o For example, if you dipped a zinc metal rod into a solution which contained zinc
ions, there would be zinc atoms losing electrons to form zinc ions and at the same
time, zinc ions gaining electrons to become zinc atoms
o This would cause a redox equilibrium
 When writing half equations for this topic, the electrons will always be written on the
left-hand side (demonstrating reduction)
 The position of equilibrium is different for different species, which is why different
species will have electrode (reduction) potentials
 The more positive (or less negative) an electrode potential, the more likely it is for that
species to undergo reduction
o The equilibrium position lies more to the right
 For example, the positive electrode potential of bromine below, suggests that it is likely
to get reduced and form bromide (Br-) ions

Br2(l) + 2e- ⇌ 2Br-(aq)        voltage = +1.09 V

 The more negative (or less positive) the electrode potential, the less likely it is that
reduction of that species will occur
o The equilibrium position lies more to the left
 For example, the negative electrode potential of sodium suggests that it is unlikely that
the sodium (Na+) ions will be reduced to sodium (Na) atoms
Na+(aq) + e- ⇌ Na(s)        voltage = -2.71 V

Standard electrode potential

 The position of equilibrium and therefore the electrode potential depends on factors such
as:
o Temperature
o Pressure of gases
o Concentration of reagents
 So, to be able to compare the electrode potentials of different species, they all have to be
measured against a common reference or standard
 Standard conditions also have to be used when comparing electrode potentials
 These standard conditions are:
o Ion concentration of 1.00 mol dm-3
o A temperature of 298 K
o A pressure of 1 atm

 The electrode potentials are measured relative to something called a standard hydrogen
electrode
 The standard hydrogen electrode is given a value of 0.00 V, and all other electrode
potentials are compared to this standard
 This means that the electrode potentials are always referred to as a standard electrode
potential (Eꝋ)
 The standard electrode potential (Eꝋ) is the voltage produced when a standard half-
cell is connected to a standard hydrogen cell under standard conditions
 For example, the standard electrode potential of bromine suggests that relative to the
hydrogen half-cell it is more likely to get reduced, as it has a more positive Eꝋ value

Br2(l) + 2e- ⇌ 2Br-(aq)        Eꝋ = +1.09 V

2H+(aq) + 2e- ⇌ H2(g)        Eꝋ = 0.00 V

 The standard electrode potential of sodium, on the other hand, suggests that relative to the
hydrogen half-cell it is less likely to get reduced as it has a more negative Eꝋ value

Na+ (aq) + e- ⇌ Na(s)        Eꝋ = -2.71 V

2H+ (aq) + 2e- ⇌ H2(g)        Eꝋ = 0.00 V

Standard cell potential

 Once the Eꝋof a half-cell is known, the voltage of an electrochemical cell made up of

two half-cells can be calculated
o These could be any half-cells and neither have to be a standard hydrogen
electrode
 This is also known as the standard cell potential (Ecellꝋ)
 o The standard cell potential is the difference in Eꝋ between two half-cells
o For example, an electrochemical cell consisting of bromine and sodium half-cells
has an Ecellꝋ of:

Ecellꝋ = (+1.09) - (-2.71)

= +3.80 V

Standard Hydrogen Electrode

 When a metal rod is placed in an aqueous solution, a redox equilibrium is established

between the metal ions and atoms
o For example, the copper atoms get oxidised and enter the solution as copper ions

Cu(s) → Cu2+(aq) + 2e-

Oxidation of copper ions

 
o The copper ions gain electrons from the metal rod and deposit as metal atoms on
the rod

Cu2+(aq) + 2e- → Cu(s)

Reduction of copper ions


o When equilibrium is established, the rate of oxidation and reduction of copper
is equal

 The position of the redox equilibrium is different for different metals

o Copper is more easily reduced, thus the equilibrium lies further over to the right

Cu2+ (aq) + 2e- ⇌ Cu (s)

 
o Vanadium is more easily oxidised, thus the equilibrium lies further over to
the left

V2+ (aq) + 2e- ⇌ V(s)

 The metal atoms and ions in solution cause an electric potential (voltage)

 This potential cannot be measured directly however the potential between the
metal/metal ion system and another system can be measured
 This value is called the electrode potential (E) and is measured in volts
o The electrode potential is the voltage measured for a half-cell compared to
another half-cell
o Often, the half-cell used for comparison is the standard hydrogen electrode

Standard hydrogen electrode

 The standard hydrogen electrode is a half-cell used as reference electrodes and

consists of:
o Hydrogen gas in equilibrium with H+ ions of concentration 1.00 mol dm-3 (at 1
atm)

2H+ (aq) + 2e- ⇌ H2 (g)


o An inert platinum electrode that is in contact with the hydrogen gas and H+ ions
 When the standard hydrogen electrode is connected to another half-cell, the standard
electrode potential of that half-cell can be read off a voltmeter
 The standard electrode potential of a half-cell can be determined by connecting it to a
standard hydrogen electrode

5.3.4 Measuring the Standard Electrode

Potential
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Measuring the Standard Electrode Potential

 There are three different types of half-cells that can be connected to a standard hydrogen
electrode
o A metal / metal ion half-cell
 o A non-metal / non-metal ion half-cell
o An ion / ion half-cell (the ions are in different oxidation states)

Metal/metal ion half-cell

 Example of a metal / metal ion half-cell connected to a standard hydrogen electrode

 An example of a metal/metal ion half-cell is the Ag+/ Ag half-cell

 o Ag is the metal
o Ag+ is the metal ion
 This half-cell is connected to a standard hydrogen electrode and the two half-equations
are:

Ag+ (aq) + e- ⇌ Ag (s)        Eꝋ = + 0.80 V

2H+ (aq) + 2e- ⇌ H2 (g)        Eꝋ = 0.00 V 

 Since the Ag+/ Ag half-cell has a more positive Eꝋ value, this is the positive pole and the
H+/H2 half-cell is the negative pole
 The standard cell potential (Ecellꝋ) is Ecellꝋ = (+ 0.80) - (0.00) = + 0.80 V
 The Ag+ ions are more likely to get reduced than the H+ ions as it has a greater Eꝋ value
o Reduction occurs at the positive pole
o Oxidation occurs at the negative pole

Non-metal/non-metal ion half-cell

 In a non-metal/non-metal ion half-cell platinum wire or foil is used as an electrode to

make electrical contact with the solution
o Like graphite, platinum is inert and does not take part in the reaction
o The redox equilibrium is established on the platinum surface
 An example of a non-metal/non-metal ion is the Br2/Br- half-cell
o Br is the non-metal
o Br- is the non-metal ion
 The half-cell is connected to a standard hydrogen electrode and the two half-equations
are:

Br2 (l) + 2e- ⇌ 2Br- (aq)        Eꝋ = +1.09 V

2H+ (aq) + 2e- ⇌ H2 (g)        Eꝋ = 0.00 V   

 The Br2/Br- half-cell is the positive pole and the H+/H2 is the negative pole

 The Ecellꝋ is: Ecellꝋ = (+ 1.09) - (0.00) = + 1.09 V
 The Br2 molecules are more likely to get reduced than H+ as they have a greater Eꝋ value
Example of a non-metal / non-metal ion half-cell connected to a standard hydrogen electrode

Ion/Ion half-cell
  A platinum electrode is again used to form a half-cell of ions that are in different
oxidation states
 An example of such a half-cell is the MnO4-/Mn2+ half-cell
o MnO4- is an ion containing Mn with oxidation state +7
o The Mn2+ ion contains Mn with oxidation state +2
 This half-cell is connected to a standard hydrogen electrode and the two half-equations
are:

MnO4- (aq) + 8H+ (aq) + 5e- ⇌ Mn2+ (aq) + 4H2O (l)       Eꝋ = +1.52 V

2H+ (aq) + 2e- ⇌ H2 (g)       Eꝋ = 0.00 V   

 The H+ ions are also present in the half-cell as they are required to convert MnO4- into
Mn2+ ions
 The MnO4-/Mn2+ - half-cell is the positive pole and the H+/H2 is the negative pole
 The Ecellꝋ is Ecellꝋ = (+ 1.09) - (0.00) = + 1.09 V
 Ions in solution half cell

Standard Cell Potential: Direction of Electron Flow & Feasibility

Direction of electron flow

 The direction of electron flow can be determined by comparing the Eꝋ values of two

half-cells in an electrochemical cell

2Cl2 (g) + 2e- ⇌ 2Cl- (aq)        Eꝋ = +1.36 V

Cu2+ (aq) + 2e- ⇌ Cu (s)        Eꝋ = +0.34 V

 The Cl2 more readily accept electrons from the Cu2+/Cu half-cell

o This is the positive pole
o Cl2 gets more readily reduced
 The Cu2+ more readily loses electrons to the Cl2/Cl- half-cell
o This is the negative pole
o Cu2+ gets more readily oxidised
 The electrons flow from the Cu2+/Cu half-cell to the Cl2/Cl- half-cell
o The flow of electrons is from the negative pole to the positive pole
 The electrons flow through the wires from the negative pole to the positive pole

Feasibility
  The Eꝋ values of a species indicate how easily they can get oxidised or reduced
 The more positive the value, the easier it is to reduce the species on the left of the half-
equation
o The reaction will tend to proceed in the forward direction
 The less positive the value, the easier it is to oxidise the species on the right of the half-
equation
o The reaction will tend to proceed in the backward direction
o A reaction is feasible (likely to occur) when the Ecellꝋ is positive
 For example, two half-cells in the following electrochemical cell are:

Cl2 (g) + 2e- ⇌ 2Cl- (aq)        Eꝋ = +1.36 V

Cu2+ (aq) + 2e- ⇌ Cu (s)        Eꝋ = +0.34 V

 Cl2 molecules are reduced as they have a more positive Eꝋ value

 The chemical reaction that occurs in this half cell is:

Cl2 (g) + 2e- → 2Cl- (aq)          

 Cu2+ ions are oxidised as they have a less positive Eꝋ value

 The chemical reaction that occurs in this half cell is:

Cu (s) → Cu2+ (aq) + 2e-

 The overall equation of the electrochemical cell is (after cancelling out the electrons):

Cu (s) + Cl2 (g) → 2Cl- (aq) + Cu2+ (aq)

OR

Cu (s) + Cl2 (g) → CuCl2 (s)

 The forward reaction is feasible (spontaneous) as it has a positive Eꝋ  value of +1.02 V

((+1.36) - (+0.34))
 The backward reaction is not feasible (not spontaneous) as it has a negative Eꝋ value of
-1.02 ((+0.34) - (+1.36))
 A reaction is feasible when the standard cell potential Eꝋ is positive

Exam Tip
Remember that the electrons only move through the wires in the external circuit and not through
the electrolyte solution.

Redox Equations

 The redox equations of an electrochemical cell can be constructed using the relevant

half-equations of the two half-cells
Constructing redox equations

 Step 1: Determine in which half-cell the oxidation and in which half-cell the reduction 
reaction takes place

Cl2 (g) + 2e- ⇌ 2Cl- (aq)        Eꝋ = +1.36 V

Zn2+ (aq) + 2e- ⇌ Zn (s)        Eꝋ = -0.76 V


o Reduction occurs in the Cl2/Cl- half-cell as it has the more positive Eꝋ value
o Oxidation occurs in the Zn+/Zn half-cell as it has the least positive Eꝋ value

 Step 2: Write down the half equations for each half-cell

o Half-equation of the Cl2/Cl- half-cell

Cl2 (g) + 2e-  → 2Cl- (aq)         


o Half-equation of the Zn+/Zn half-cell

Zn (s)   → Zn2+ (aq) + 2e-

 Step 3: Balance the number of electrons in both half-equations

o The number of electrons is already balanced in both half-equations as they both
contain two electrons

 Step 4 - Add up the two half-equations

Cl2 (g) + 2e-  → 2Cl- (aq)         

Zn (s)   → Zn2+ (aq) + 2e-

______________________________________ +

Cl2 (g) + Zn (s) + 2e → 2Cl- (aq) + Zn2+ (aq) + 2e-

 Step 5 - Cancel out the electrons (and H+ ions and H2O molecules if any present) to find
the overall redox reaction

Cl2 (g) + Zn (s) → 2Cl- (aq) + Zn2+ (aq)

OR

Cl2 (g) + Zn (s) → ZnCl2 (s)

Worked example: Constructing redox reactions

Answer

 Step 1:

Determine in which cell oxidation and in which cell reduction takes place

Reduction occurs in the Ag+/Ag half-cell as it has the most positive Eꝋ value

Oxidation occurs in the MnO4-/ Mn2+ half-cell as it has the least positive Eꝋ value

 Step 2:

Write down the half-equations for each cell

The half-equation for the Ag+/Ag half-cell is:

Ag+ (aq) + e- → Ag (s)             

The half-equation for the MnO4-/ Mn2+  half-cell is:

Mn2+ (aq) + 4H2O (l) → MnO4- (aq) + 8H+ (aq) + 5e-

 Step 3:
 Balance the number of electrons in both half-equations

Multiply the half-equation for the Ag+/Ag half-cell by 5 so that both half-equations
contain 5 electrons

This gives: 5Ag+ (aq) + 5e- → 5Ag (s)

 Step 4:

Add the two half-equations

5Ag+ (aq) + 5e-  + Mn2+ (aq) + 4H2O (l) → 5Ag (s) + MnO4- (aq) + 8H+ (aq) + 5e-     

 Step 5:

Cancel out the electrons to find the overall redox equation

5Ag+ (aq) + 5e-  + Mn2+ (aq) + 4H2O (l) → 5Ag (s) + MnO4- (aq) + 8H+ (aq) + 5e-     
The fully balanced redox equation is:

5Ag+ (aq) + Mn2+ (aq) + 4H2O (l) → 5Ag (s) + MnO4- (aq) + 8H+ (aq)

5.4.1 Electrolysis: Calculations

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Calculations in Electrolysis

 Faraday’s constant can be used to calculate:

o The mass of a substance deposited at an electrode
o The volume of gas liberated at an electrode

Calculating the mass of a substance deposited at an electrode

 To calculate the mass of a substance deposited at the electrode, you need to be able to:
o Write the half-equation at the electrode
o Determine the number of coulombs needed to form one mole of substance at the
specific electrode using Faraday’s constant
o Calculate the charge transferred during electrolysis
o Use simple proportion and the relative atomic mass of the substance to find its
mass
Worked example: Calculating the mass of a substance deposited at an
electrode

Answer

The magnesium (Mg2+) ion is a positively charged cation that will move towards the cathode.

 Step 1: Write the half-equation at the cathode

Mg2+(aq)          +          2e-       →         Mg(s)

1 mol                           2 mol               1 mol

 Step 2: Determine the number of coulombs required to deposit one mole of magnesium
at the cathode

For every one mole of electrons, the number of coulombs needed is 96 500 C mol-1

In this case, there are two moles of electrons required

So, the number of coulombs needed is:

F = 2 x 96 500

F = 193 000 C mol-1

 Step 3: Calculate the charge transferred during the electrolysis

Q = I x t

Q = 2.20 x (60 x 15)

= 1980 C 
  Step 4: Calculate the mass of magnesium deposited by simple proportion using the
relative atomic mass of Mg

Calculating the mass of a substance deposited at an electrode table

Therefore, 0.25 g of magnesium is deposited at the cathode

Calculating the volume of gas liberated at an electrode

 To calculate the volume of gas liberated at an electrode, you need to be able to:
o Write the half-equation at the electrode
o Determine the number of coulombs needed to form one mole of substance at the
specific electrode using Faraday’s constant
o Calculate the charge transferred during electrolysis
o Use simple proportion and the relationship 1 mol of gas occupies 24.0 dm3 at
room temperature

Worked example: Calculating the volume of a gas produced at an

electrode
Answer

The oxygen gas is formed from the oxidation of negatively charged hydroxide (OH-) ions at the
anode-

 Step 1: Write the half-equation at the anode

4OH-(aq)         →         O2(g)               +          2H2O(l)            +          4e-

4 mol                           1 mol                           2 mol                           4 mol

 Step 2: Determine the number of coulombs required to form one mole of oxygen gas at
the anode

For every one mole of electrons, the number of coulombs needed is 96 500 C mol-1

So, for four moles of electrons, the number of coulombs needed is:

F = 4 x 96 500

F = 386 000 C mol-1

 Step 3: Calculate the charge transferred during the electrolysis

Q = I x t

Q = 0.75 x (60 x 35)

= 1575 C

 Step 4: Calculate the volume of oxygen liberated by simple proportion using the
relationship 1 mol of gas occupies 24.0 dm3 at room temperature
Calculating the volume of a gas liberated at an electrode table

Therefore, 0.0979 dm3  of oxygen is formed at the anode

Worked example: Calculating the volume of hydrogen gas produced at

an electrode
The hydrogen gas is formed from the reduction of positively charged hydrogen (H+) ions at the
cathode

 Step 1: Write the half-equation at the cathode

2H+ (aq)   +     2e-       →         H2 (g)              

2 mols             2 mols             1 mol   

 Step 2: Determine the number of coulombs required to form one mole of hydrogen gas at
the cathode

For every one mole of electrons, the number of coulombs needed is:

F = 96 500 C mol-1

F = 1 x 96 500

F = 96 500 C

So, for two moles of electrons, the number of coulombs needed is:

F = 2 x 96 500

F = 193 000 C

  Step 3: Calculate the charge transferred during the electrolysis

 Q = I x t

Q = 3.25 x (60 x 17.5)

= 3 413 C

 Step 4: Calculate the volume of hydrogen liberated by simple proportion using the
relationship 1 mol of gas occupies 24.0 dm3 at room temperature

Calculating the volume of hydrogen gas produced at an electrode table

Therefore, 0.42 dm3 of hydrogen is formed at the cathode

5.4.2 Standard Cell Potential: Calculations,

Electron Flow & Feasibility
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Calculating Standard Cell Potential

  Once the standard electrode potentials (Eꝋ) of the half-cells are determined, the standard
cell potential (Ecellꝋ) can be calculated by subtracting the less positive Eꝋ from the more
positive Eꝋ value
o The half-cell with the more positive Eꝋ value will be the positive pole
o The half-cell with the less positive Eꝋ value will be the negative pole

Worked example: Calculating the standard cell potential

Answer

 Step 1: Calculate the standard cell potential

Ecellꝋ = (+0.34) - (-0.76)

= +1.10 V

The voltmeter will therefore read off a value of 1.10 V

 Step 2: Determine the positive and negative poles

The Cu2+/Cu  half-cell is the positive pole as its Eꝋ is more positive than the Eꝋ value of the
Zn2+/Zn half-cell

5.4.3 Electrochemical Series & Redox

Equations
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Electrochemical Series

 The Eꝋ values of a species indicate how easily they can get oxidised or reduced

 In other words, they indicate the relative reactivity of elements, compounds and ions
as oxidising agents or reducing agents
 The electrochemical series is a list of various redox equilibria in order of
decreasing Eꝋ values
 More positive (less negative) Eꝋ values indicate that:
o The species is easily reduced
o The species is a better oxidising agent
 Less positive (more negative) Eꝋ values indicate that:
o The species is easily oxidised
o The species is a better reducing agent
 Example of an electrochemical series in which the equilibria are arranged in order of 
decreasing Eꝋ values 

5.4.4 Non-Standard Conditions

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Effect of Concentration on Electrode Potential

 Changes in temperature and concentration of aqueous ions will affect the standard

electrode potential (Eꝋ) of a half-cell
 Under these non-standard conditions, E is used as a symbol for the electrode potential
instead of Eꝋ

Increasing the concentration of the species on the left

 If the concentration of the species on the left is increased, the position of equilibrium will
shift to the right
 This means that the species on the left gets more easily reduced
 The E value becomes more positive (or less negative)
 Let’s look at the half-cell below as an example

Zn2+ (aq) + 2e- ⇌ Zn (s)        Eꝋ = -0.76 V

 If the concentration of Zn2+ (species on the left) is increased, the equilibrium position

will shift to the right
 The species on the left (Zn2+) will get more easily reduced
 Therefore, the E value becomes less negative and will change too, for example, -0.50 V
instead
 This principle can also be applied to a half-cell with a positive Eꝋ value such as:

Fe3+ (aq) + e- ⇌ Fe2+ (aq)        Eꝋ = +0.77 V

 If the concentration of Fe3+ (species on the left) is increased, the equilibrium position

will shift to the right
 The species on the left (Fe3+) will get more easily reduced
 Therefore, the E value becomes more positive and will change too, for example, +0.89 V
instead

Increasing the concentration of species on the right

 If the concentration of the species on the right is increased, the position of equilibrium
will shift to the left
 This means that the species on the left gets less easily reduced
 The E value becomes less positive (or more negative)
 Let’s look again at the half-cell below

Zn2+ (aq) + 2e- ⇌ Zn (s)        Eꝋ = -0.76 V

 If the concentration of Zn (species on the right) is increased, the equilibrium position

will shift to the left
  The species on the left (Zn2+) will get less easily reduced
 Therefore, the E value becomes more negative and will change too, for example, -0.82 V
instead
 This principle can, again, also be applied to a half-cell with a positive Eꝋ value:

Fe3+ (aq) + e- ⇌ Fe2+ (aq)        Eꝋ = +0.77 V

 If the concentration of Fe2+ (species on the right) is increased, the equilibrium position

will shift to the left
 The species on the left (Fe3+) will get less easily reduced
 Therefore, the E value becomes less positive and will change too, for example, +0.56 V
instead

Effect of concentration on the electrode potential

5.4.5 Nernst Equation

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The Nernst Equation

  Under non-standard conditions, the cell potential of the half-cells is shown by the
symbol Ecell
 The effect of changes in temperature and ion concentration on the Ecell can be deduced
using the Nernst equation

E = electrode potential under nonstandard conditions

E⦵ = standard electrode potential

R = gas constant (8.31 J K-1 mol-1)

T = temperature (kelvin, K)

z = number of electrons transferred in the reaction

F = Faraday constant (96 500 C mol-1)

ln = natural logarithm

 This equation can be simplified to


o At standard temperature, R, T and F are constant
o ln x = 2.303 log10 x
 The Nernst equation only depends on aqueous ions and not solids or gases
 The concentrations of solids and gases are therefore set to 1.0 mol dm-3

Applying Nernst equation

 The concentrations of ions for the Fe3+/Fe2+ half-cell are as follows:

Fe3+ (aq) + e- ⇌ Fe2+ (aq)

[Fe3+] = 0.034 mol dm-3

[Fe2+] = 0.64 mol dm-3 

  The Nernst equation for this half-reaction is, therefore:


o The oxidised species is Fe3+ as it has a higher oxidation number (+3)
o The reduced species is Fe2+ as it has a lower oxidation number (+2)
o z is 1 as only one electron is transferred in this reaction

 An example of a half-cell in which two electrons are transferred is the Cu2+/Cu half-cell

Cu2+ (aq) + 2e- ⇌ Cu (s)

[Cu2+] = 0.0010 mol dm-3

 The Nernst equation for this half-reaction is:


o The oxidised species is Cu2+ as it has a higher oxidation number (+2)
o The reduced species is Cu as it has a lower oxidation number (0)
o Cu is a solid and is not included in the Nernst equation (its concentration doesn’t
change)
o z is 2 as 2 electrons are transferred in this reaction

Worked example: Calculating the electrode potential of a Fe 3+/Fe2+ half-

cell
Answer

= (+0.77) + (-0.075)

= +0.69 V

Worked example: Calculating the electrode potential of a Cu2+/Cu half-

cell
Answer

= (+0.34) + (-0.089)

= +0.25 V

Exam Tip
Make sure you always check what the temperature is. If the temperature is not 298 K (or 25 oC)
the full Nernst equation should be used.You don’t need to know how to simplify the Nernst
equation to
You are only expected to use the equation when the temperature is 298 K (or 25 oC).

5.4.6 Standard Electrode Potentials: Free

Energy Change
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Calculating Free Energy Change Using Standard Electrode Potentials

 The standard free energy change can be calculated using the standard cell potential of
an electrochemical cell

ΔGꝋ = - n x Ecellꝋ x F

ΔGꝋ = standard Gibbs free energy

n = number of electrons transferred in the reaction

Ecellꝋ = standard cell potential (V)

F = Faraday constant (96 500 C mol-1)

Worked Example: Calculating the standard Gibbs free energy change

Answer

 Step 1: Determine the two half-equations and their Eꝋ using the Data booklet

Fe3+ (aq) + e- ⇌ Fe2+ (aq)        Eꝋ = +0.77 V

Cu2+ (aq) + 2e- ⇌ Cu (s)       Eꝋ = +0.34 V 

 Step 2 : Calculate the Ecellꝋ

Ecellꝋ = Eredꝋ - Eoxꝋ

= (+0.77) - (+0.34)

= +0.43 V

 Step 3: Determine the number of electrons transferred in the reaction

The Cu2+/Cu has a smaller Eꝋ value which means that it gets oxidised

It transfers two electrons to  two Fe3+ ions

Each Fe3+ ion accepts one electron so the total number of electrons transferred is two

 Step 4: Substitute the values in for the standard Gibbs free energy equation

ΔGꝋ = - n x Ecellꝋ x F

= -2 x (+0.43) x 96 500
 
= -82 990 J mol-1

= -83 kJ mol-1

5.5.1 Acids & Bases

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Conjugate Acids & Bases

 A Brønsted acid is a species that can donate a proton

o For example, hydrogen chloride (HCl) is a Brønsted acid as it can lose a proton to
form a hydrogen (H+) and chloride (Cl-) ion

            HCl (aq) → H+ (aq) + Cl- (aq)

 A Brønsted base is a species that can accept a proton

o For example, a hydroxide (OH-) ion is a Brønsted base as it can accept a proton to
form water

OH- (aq) + H+ (aq) → H2O (l)

 In an equilibrium reaction, the products are formed at the same rate as the reactants are
used
 This means that at equilibrium, both reactants and products are present in the solution
 For example, ethanoic acid (CH3COOH) is a weak acid that partially dissociates in
solution
 When equilibrium is established there are CH3COOH, H2O, CH3COO- and H3O+ ions
present in the solution
 The species that can donate a proton are acids and the species that can accept a proton
are bases

 The reactant CH3COOH is linked to the product CH3COO- by the transfer of

a proton from the acid (CH3COOH) to the base (CH3COO-)
 Similarly, the H2O molecule is linked to H3O+ ion by the transfer of a proton
 These pairs are therefore called conjugate acid-base pairs
 A conjugate acid-base pair is two species that are different from each other by an H+ ion
 o Conjugate here means related
o In other words, the acid and base are related to each other by one proton
difference

Defining Conjugate Acids & Bases

 Conjugate acid-base pairs are a pair of reactants and products that are linked to each
other by the transfer of a proton
 For example, in the equilibrium reaction below, the propanoic acid (CH3CH2COOH)
partially dissociates in solution to form propanoate (CH3CH2COO-) and hydrogen (H+)
ions
 When equilibrium is established there are CH3COOH, H2O, CH3COO- and H3O+ ions
present in the solution
 The species that can donate a proton are acids and the species that can accept a proton
are bases

 In the forward reaction:
o The acid CH3CH2COOH is linked to the base CH3CH2COO-
o CH3CH2COO- is, therefore, the conjugate base of CH3CH2COOH

CH3CH2COOH - CH3CH2COO- = conjugate acid-base pair


o The base H2O is linked to the acid H3O+
o H3O+ is, therefore, the conjugate acid of H2O

H2O - H3O+ = conjugate acid-base pair

 In the reverse reaction
o The base CH3CH2COO- is linked to the acid CH3CH2COOH
o CH3CH2COOH is therefore conjugate acid of CH3CH2COO-

CH3CH2COO- - CH3CH2COOH = conjugate acid-base pair


o The acid H3O+ is linked to the base H2O
o H2O is, therefore, the conjugate base of H3O+

H3O+ - H2O = conjugate acid-base pair

Worked Example: Identifying conjugate acid-base pairs

Answer

 In the forward reaction:

o NH4+ is the conjugate acid of the base NH3
o OH- is the conjugate base of the acid H2O
 In the reverse reaction
o NH3 is the conjugate base of the acid NH4+
o H2O is the conjugate acid of the base OH-
5.5.2 pH, Ka, pKa & Kw Calculations
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Calculating pH, Ka, pKA & Kw

pH

 The pH indicates the acidity or basicity of an acid or alkali

 The pH scale goes from 0 to 14
o Acids have pH between 0-7
o Pure water is neutral and has a pH of 7
o Bases and alkalis have pH between 7-14
 The pH can be calculated using: pH = -log10 [H+]

where [H+] = concentration of H+ ions (mol dm-3)

 The pH can also be used to calculate the concentration of H+ ions in solution by

rearranging the equation to:

[H+] = 10-pH

Worked Example: Calculating the pH of acids

Answer

pH = -log [H+]

= -log 1.32 x 10-3

= 2.9
Ka & pKa

 The Ka is the acidic dissociation constant

o It is the equilibrium constant for the dissociation of a weak acid at 298 K
 For the partial ionisation of a weak acid HA the equilibrium expression to find Ka is as
follows:

HA (aq) ⇌ H+ (aq) + A- (aq)

 When writing the equilibrium expression for weak acids, the following assumptions are
made:
o The concentration of hydrogen ions due to the ionisation of water is negligible
o The dissociation of the weak acid is so small that the concentration of HA is
approximately the same as the concentration of A-
 The value of Ka indicates the extent of dissociation
o A high value of Ka means that:
 The equilibrium position lies to the right
 The acid is almost completely ionised
 The acid is strongly acidic
o A low value of Ka means that:
 The equilibrium position lies to the left
 The acid is only slightly ionised (there are mainly HA and only a few
H+ and A- ions)
 The acid is weakly acidic

 Since Ka values of many weak acids are very low, pKa values are used instead to compare
the strengths of weak acids with each other

pKa = -log10 Ka

 The less positive the pKa value the more acidic the acid is

Worked Example: Calculating the Ka & pKa of weak acids

Answer

 Step 1: Write down the equation for the partial dissociation of ethanoic acid

CH3COOH (aq) ⇌ H+ (aq) + CH3COO- (aq)

 Step 2: Write down the equilibrium expression to find Ka

 Step 3: Simplify the expression

The ratio of H+ to CH3COO- is 1:1

The concentration of H+ and CH3COO- is, therefore, the same

The equilibrium expression can be simplified to:

 Step 4: Substitute the values into the expression to find Ka

 = 1.74 x 10-5

 Step 5: Determine the units of Ka

= mol dm-3

The value of Ka is therefore 1.74 x 10-5 mol dm-3

 Step 6: Find pKa

pKa = - log10 Ka

= - log10 (1.74 x 10-5)

= 4.76

Kw

 The Kw is the ionic product of water

o It is the equilibrium constant for the dissociation of water at 298 K
o Its value is 1.00 x 10-14 mol2 dm-6
 For the ionisation of water the equilibrium expression to find Kw is as follows:

H2O (l) ⇌ H+ (aq) + OH- (aq)

  As the extent of ionisation is very low, only small amounts of H+ and  OH- ions are
formed
 The concentration of H2O can therefore be regarded as constant and removed from
the Kw expression
 The equilibrium expression therefore becomes:

Kw = [H+] [OH-]

 As the [H+] = [OH+] in pure water, the equilibrium expression can be further simplified to:

Kw = [H+]2

Worked Example: Calculating the concentration of H+ of pure water

Answer

 Step 1: Write down the equation for the partial dissociation of water

 In pure water, the following equilibrium exists:

H2O (l) ⇌ H+ (aq) + OH- (aq)

 Step 2: Write down the equilibrium expression to find Kw

 Step 3: Simplify the expression

Since the concentration of H2O is constant, this expression can be simplified to:

Kw = [H+] [OH-]

  Step 4: Further simplify the expression

The ratio of H+ to OH- is 1:1

The concentration of H+ and OH- is, therefore, the same and the equilibrium expression can be
further simplified to:

Kw = [H+]2

 Step 5: Rearrange the equation to find [H+]

Kw = [H+]2

 Step 6: Substitute the values into the expression to find Kw

= 1.00 x 10-7 mol dm-3

Exam Tip
Remember:The greater the Ka value, the more strongly acidic the acid is.The greater the
pKa value, the less strongly acidic the acid is.Also, you should be able to rearrange the following
expressions:

pH = -log10 [H+] TO [H+] = 10-pH

pKa = - log10 Ka TO Ka = 10-pKa

5.5.3 pH & [H+] Calculations

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Calculating [H+] & pH

  If the concentration of H+ of an acid or alkali is known, the pH can be calculated using
the equation:

pH = -log [H+]

 Similarly, the concentration of H+ of a solution can be calculated if the pH is known by

rearranging the above equation to:

[H+] = 10-pH

Strong acids

 Strong acids are completely ionised in solution

HA (aq) → H+ (aq) + A- (aq)

 Therefore, the concentration of hydrogen ions ([H+]) is equal to the concentration of acid
([HA])
 The number of hydrogen ions ([H+]) formed from the ionisation of water is very
small relative to the [H+] due to ionisation of the strong acid and can therefore
be neglected
 The total [H+] is therefore the same as the [HA]

Worked Example: pH calculations of a strong acid

Answer

Hydrochloric acid is a strong monobasic acid

 HCl (aq) → H+ (aq) + Cl- (aq)

Answer 1

The pH of the solution is:

pH = -log [H+]

= -log 1.6 x 10-4

= 3.80

Answer 2

The hydrogen concentration can be calculated by rearranging the equation for pH

pH = -log [H+]

[H+] = 10-pH

= 10-3.1

= 7.9 x 10-4 mol dm-3

Strong alkalis

 Strong alkalis are completely ionised in solution

BOH (aq) → B+ (aq) + OH- (aq)

 Therefore, the concentration of hydroxide ions ([OH-]) is equal to the concentration of

base ([BOH])
o Even strong alkalis have small amounts of H+ in solution which is due to the
ionisation of water
 The concentration of OH- in solution can be used to calculate the pH using the ionic
product of water

Kw = [H+] [OH-]

 Since Kw is 1.00 x 10-14 mol2 dm-6

  Once the [H+] has been determined, the pH of the strong alkali can be founding using pH
= -log[H+]
 Similarly, the ionic product of water can be used to find the concentration of OH- ions in
solution if [H+] is known

Worked Example: pH calculations of a strong alkali

Answer

Sodium hydroxide is a strong base which ionises as follows:

NaOH (aq) → Na+ (aq) + OH- (aq) 

Answer 1

The pH of the solution is:

pH = -log [H+]
= -log 3.5 x 10-11

= 10.5

Answer 2

  Step 1: Calculate hydrogen concentration by rearranging the equation for pH

pH = -log [H+]

= 10-pH

= 10-12.3

= 5.01 x 10-13 mol dm-3

 Step 2: Rearrange the ionic product of water  to find the concentration of hydroxide

ions

Kw = [H+] [OH-]

 Step 3: Substitute the values into the expression to find the concentration of hydroxide
ions

Since Kw is 1.00 x 10-14 mol2 dm-6

= 0.0199 mol dm-3

Weak acids

 The pH of weak acids can be calculated when the following is known:

o The concentration of the acid
o The Ka value of the acid
Worked Example: pH calculations of weak acids

Answer

Ethanoic acid is a weak acid which ionises as follows:

CH3COOH (aq) ⇌ H+ (aq) + CH3COO- (aq)

 Step 1: Write down the equilibrium expression to find Ka

 Step 2: Simplify the expression

The ratio of H+ to CH3COO- ions is 1:1

The concentration of H+ and CH3COO- ions are therefore the same

The expression can be simplified to:

 Step 3: Rearrange the expression to find [H+]

  Step 4: Substitute the values into the expression to find [H+]

= 1.32 x 10-3 mol dm-3

 Step 5: Find the pH

pH = -log10 [H+]

= -log10 1.32 x 10-3

= 2.88

5.5.4 Buffers
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Buffers

 A buffer solution is a solution in which the pH does not change a lot when small
amounts of acids or alkalis are added
o A buffer solution is used to keep the pH almost constant
o A buffer can consists of weak acid - conjugate base or weak base - conjugate
acid

Ethanoic acid & sodium ethanoate as a buffer

 A common buffer solution is an aqueous mixture of ethanoic acid and sodium

ethanoate
 Ethanoic acid is a weak acid and partially ionises in solution to form a relatively low
concentration of ethanoate ions
 Sodium ethanoate is a salt which fully ionises in solution

 There are reserve supplies of the acid (CH3COOH) and its conjugate base (CH3COO-)
o The buffer solution contains relatively high concentrations of CH3COOH (due to
ionisation of ethanoic acid) and CH3COO- (due to ionisation
of sodium ethanoate)
 In the buffer solution, the ethanoic acid is in equilibrium with hydrogen and ethanoate
ions

 When H+ ions are added:

 The equilibrium position shifts to the left as H+ ions react with CH3COO- ions to form
more CH3COOH until equilibrium is re-established
 As there is a large reserve supply of CH3COO- the concentration of CH3COO- in solution
doesn’t change much as it reacts with the added H+ ions
 As there is a large reserve supply of CH3COOH the concentration of CH3COOH in
solution doesn’t change much as CH3COOH is formed from the reaction of
CH3COO- with H+
 As a result, the pH remains reasonable constant
 When hydrogen ions are added to the solution the pH of the solution would decrease;
However, the ethanoate ions in the buffer solution react with the hydrogen ions to prevent this
and keep the pH constant

 When OH- ions are added:

 The OH- reacts with H+ to form water

OH- (aq) + H+  (aq) → H2O (l)

 The H+ concentration decreases
 The equilibrium position shifts to the right and more CH3COOH molecules ionise to form
more H+ and CH3COO- until equilibrium is re-established

CH3COOH (aq) → H+ (aq) + CH3COO- (aq)

 As there is a large reserve supply of CH3COOH the concentration of CH3COOH in

solution doesn’t change much when CH3COOH dissociates to form more H+ ions
 As there is a large reserve supply of CH3COO- the concentration of CH3COO- in solution
doesn’t change much
 As a result, the pH remains reasonable constant
 When hydroxide ions are added to the solution, the hydrogen ions react with them to form
water; The decrease in hydrogen ions would mean that the pH would increase however the
equilibrium moves to the right to replace the removed hydrogen ions and keep the pH constant

Uses of buffer solutions in controlling the pH of blood

 In humans, HCO3- ions act as a buffer to keep the blood pH between 7.35 and 7.45
 Body cells produce CO2 during aerobic respiration
 This CO2 will combine with water in blood to form a solution containing H+ ions

CO2 (g) + H2O (l) ⇌ H+ (aq) + HCO3- (aq)

 This equilibrium between CO2 and HCO3- is extremely important

 If the concentration of H+ ions is not regulated, the blood pH would drop and cause
‘acidosis’
o Acidosis refers to a condition in which there is too much acid in the body fluids
such as blood
o This could cause body malfunctioning and eventually lead to coma
 If there is an increase in H+ ions
 The equilibrium position shifts to the left until equilibrium is restored

H+ (aq) + HCO3- (aq) → CO2 (g) + H2O (l)

 This reduces the concentration of H+ and keeps the pH of the blood constant

 If there is a decrease in H+ ions
o The equilibrium position shifts to the right until equilibrium is restored
 CO2 (g) + H2O (l) → H+ (aq) + HCO3- (aq)

 This increases the concentration of H+ and keeps the pH of the blood constant

Exam Tip
Remember that buffer solutions cannot cope with excessive addition of acids or alkalis as their
pH will change significantly.The pH will only remain relatively constant if small amounts of
acids or alkalis are added.

5.5.5 Buffer Calculations

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Calculating pH of Buffer Solutions

 The pH of a buffer solution can be calculated using:

o The Ka of the weak acid
o The equilibrium concentration of the weak acid and its conjugate base (salt)
 To determine the pH, the concentration of hydrogen ions is needed which can be found
using the equilibrium expression

 To simplify the calculations, logarithms are used such that the expression becomes:

 Since -log10 [H+] = pH, the expression can also be rewritten as:

Worked Example: Calculating the pH of a buffer solution

Answer

Ethanoic acid is a weak acid that ionises as follows:

CH3COOH (aq) ⇌ H+ (aq) + CH3COO- (aq)

 Step 1: Write down the equilibrium expression to find Ka

 Step 2: Rearrange the equation to find [H+]

 Step 3: Substitute the values into the expression

= 8.39 x 10-6 mol dm-3

 Step 4: Calculate the pH

 pH = - log [H+]

= -log 8.39 x 10-6

= 5.08

5.5.6 Solubility Product

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Solubility Product

 Solubility is defined as the number of grams or moles of compound needed

to saturate 100 g of water, or it can also be defined in terms of 1 kg of water, at a given
temperature
o For example, sodium chloride (NaCl) is considered to be a soluble salt as a
saturated solution contains 36 g of NaCl per 100 g of water
o Lead chloride (PbCl2) on the other hand is an insoluble salt as a saturated solution
only contains 0.99 g of PbCl2 per 100 g of water

Solubility product

 The solubility product (Ksp) is:

o The product of the concentrations of each ion in a saturated solution of a
relatively soluble salt
o At 298 K
o Raised to the power of their relative concentrations

C (s) ⇌ aAx+ (aq) + bBy- (aq)

Ksp = [Ax+ (aq)]a [By- (aq)]b

 When an undissolved ionic compound is in contact with a saturated solution of its

ions, an equilibrium is established
 The ions move from the solid to the saturated solution at the same rate as they move from
the solution to the solid
o For example, the undissolved magnesium chloride (MgCl2) is in equilibrium with
a saturated solution of its ions

MgCl2 (s) ⇌ Mg2+ (aq) + 2Cl- (aq)

 When the undissolved MgCl2 salt gets in contact with its ions in a saturated solution, an
equilibrium between the salt and ions is established


o The solubility product for this equilibrium is:

Ksp = [Mg2+ (aq)] [Cl- (aq)]2

 The Ksp is only useful for sparingly soluble salts

 The smaller the value of Ksp, the lower the solubility of the salt

Expressing Ksp

 The general equilibrium expression for the solubility product (Ksp) is:

C (s) ⇌ aAx+ (aq) + bBy- (aq)

Ksp = [Ax+ (aq)]a [By- (aq)]b

Worked Example: Expressing Ksp of ionic compounds

Answer

Expressing Ksp of ionic compounds answers table

5.5.7 Solubility Product Calculations
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Calculating the Solubility Product

 Calculations involving the solubility product (Ksp) may include::

o Calculating the solubility product of a compound from its solubility
o Calculating the solubility of a compound from the solubility product

Worked example: Calculating the solubility product of a compound from

its solubility
Answer

 Step 1: Write down the equilibrium equation

PbBr2 (s) ⇌ Pb2+ (aq) + 2Br- (aq)

 Step 2: Write down the equilibrium expression

Ksp = [Pb2+(aq)] [Br- (aq)]2

 Step 3: Calculate the ion concentrations in the solution

[PbBr2(s)] = 1.39 x 10-3 mol dm-3

The ratio of PbBr2 to Pb2+ is 1:1

[Pb2+(aq)] = [PbBr2(s)] = 1.39 x 10-3 mol dm-3

The ratio of PbBr2 to Br- is 1:2

[Br-(aq)] = 2 x [PbBr2(s)] = 2 x 1.39 x 10-3 mol dm-3

= 2.78 x 10-3 mol dm-3

 Step 4: Substitute the values into the expression to find the solubility product

Ksp = (1.39 x 10-3) x (2.78 x 10-3)2

= 1.07 x 10-8

 Step 6:  Determine the correct units of Ksp

Ksp = (mol dm-3) x (mol dm-3)2

 = mol3 dm-9

The solubility product is therefore 1.07 x 10-8 mol3 dm-9

Worked example: Calculating the solubility of a compound from its

solubility product

Answer

 Step 1: Write down the equilibrium equation

CuO (s) ⇌ Cu2+ (aq) + O2- (aq)

 Step 2: Write down the equilibrium expression

Ksp = [Cu2+ (aq)] [O2- (aq)]

 Step 3: Simplify the equilibrium expression

The ratio of Cu2+ to O2- is 1:1

[Cu2+(aq)] = [O2-(aq)] so the expression can be simplified to:

Ksp = [Cu2+ (aq)]2

 Step 4: Substitute the value of Ksp into the expression to find the concentration

5.9 x 10-36 = [Cu2+ (aq)]2

= 2.4 x 10-18 mol dm-3

Since [CuO(s)] = [Cu2+ (aq)] the solubility of copper oxide is 2.4 x 10-18 mol dm-3

Exam Tip
Remember that the solubility product is only applicable to very slightly soluble salts and cannot
be used for soluble salts such as:

 Group 1 element salts

 All nitrates salts
 All ammonium salts
 Many sulfate salts
 Many halide salts (except for lead(II) halides and silver halides)

5.5.8 The Common Ion Effect

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Solubility Product & the Common Ion Effect

 A saturated solution is a solution that contains the maximum amount of dissolved salt

 If a second compound, which has an ion in common with the dissolved salt, is added to
the saturated solution, the solubility of the salt reduces and a solid precipitate will be
formed
 This is also known as the common ion effect
 For example, if a solution of potassium chloride (KCl) is added to a saturated solution
of silver chloride (AgCl) a precipitate of silver chloride will be formed
o The chloride ion is the common ion
 The solubility product can be used to predict whether a precipitate will actually form or
not
o A precipitate will form if the product of the ion concentrations is greater than the
solubility product (Ksp)

Common ion effect in silver chloride

 When a KCl solution is added to a saturated solution of AgCl, an AgCl precipitate forms

 In a saturated AgCl solution, the silver chloride is in equilibrium with its ions

AgCl (s) ⇌ Ag+ (aq) + Cl- (aq)

 When a solution of potassium chloride is added:

o Both KCl and AgCl have the common Cl- ion
o There is an increased Cl- concentration so the equilibrium position shifts to the left
o The increase in Cl- concentration also means that [Ag+ (aq)] [Cl-(aq)]
is greater than the Ksp for AgCl
 o As a result, the AgCl is precipitated

The addition of potassium chloride to a saturated solution of silver chloride results in the
precipitate of silver chloride

Worked Example: Calculations using the Ksp values and the

concentration of the common ion
Answer

 Step 1: Determine the equilibrium reaction of CaSO4

CaSO4 (s) ⇌ Ca2+ (aq) + SO42- (aq)

 Step 2: Write down the equilibrium expression for Ksp

Ksp = [Ca2+ (aq)] [SO42- (aq)]

 Step 3: Determine the concentrations of the ions

There are equal volumes of each solution

This means that the total solution was diluted by a factor of 2

The new concentrations of the ions are there halved

= 5.0 x 10-4 mol dm-3

 Step 4: Substitute the values into the expression

Product of the ion concentrations = [Ca2+ (aq)] x [SO42- (aq)]

= (5.0 x 10-4) x (5.0 x 10-4)

= 2.5 x 10-7 mol2 dm-6
  Step 5: Determine if a precipitate will form

As the product of the ion concentration (2.5 x 10-7 mol dm-3 ) is smaller than the Ksp value (2.0 x
10-5 mol2 dm-6), the CaSO4 precipitate will not be formed

5.5.9 Partition Coefficients

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Partition Coefficient & Calculations

 The partition coefficient (Kpc) is the ratio of the concentrations of a solute in two

different immiscible solvents in contact with each other when equilibrium has been
established (at a particular temperature)
 For example, methylamine (CH3NH2) is dissolved in two immiscible solvents:
o Water
o An organic solvent
 A separating funnel is shaken with the organic solvent and aqueous methylamine
 The methylamine is soluble in both solvents, so when the mixture is left to settle
an equilibrium is established
o The rate of methylamine molecules moving from the organic layer into the
aqueous layer is equal to the rate of molecules moving from the aqueous layer to
the organic layer

CH3NH2(aq) ⇌ CH3NH2(organic solvent)

 The value of its equilibrium constant is also called the partition coefficient

 The partition coefficient is the ratio of methylamine molecules in the organic and aqueous
layer once equilibrium has been established

Calculating Partition Coefficients

  The partition coefficient (Kpc) for a system in which the solute is in the same physical
state in the two solvents can be calculated using the equilibrium expression

Worked example: Calculating the partition coefficient

Answer

 Step 1: Write down the equilibrium equation

CH3NH2(aq) ⇌ CH3NH2(organic solvent)

 Step 2: Write down the equilibrium expression 

  Step 3: Determine how many moles of CH3NH2 has reacted with HCl at the end-point

At the end-point, all CH3NH2 (aq) has been neutralised by HCl (aq)

CH3NH2 (aq) + HCl (aq) → CH3NH3Cl (aq)

CH3NH2 and HCl react in a ratio of 1:1

Mol (HCl) = mol (CH3NH2) = 0.225 x 0.0141

= 3.18 x 10-3 mol

 Step 4: Determine the number of moles of CH3NH2 present in the aqueous layer

Only 50.0 cm3 of the aqueous layer was used to titrate against HCl

Thus, 3.18 x 10-3 mol of CH3NH2 was present in only 50.0 cm3 of the aqueous layer

The number of moles of CH3NH2 in 100 cm3 aqueous layer is, therefore:

Mol (CH3NH2 aqueous layer) = 3.18 x 10-3 x 2 = 6.34 x 10-3 mol

 Step 5: Determine the number of moles of CH3NH2 in the organic layer

Mol CH3NH2 (organic layer) = mol CH3NH2 (total) - mol CH3NH2(aqueous layer)

Mol CH3NH2 (total) = 0.100 x 0.150 = 0.015 mol

Mol CH3NH2 (organic layer) = 0.015 - 6.34 x 10-3 = 8.67 x 10-3 mol

 Step 6: Change the number of moles into concentrations

= 0.063 mol dm-3

= 0.116 mol dm-3

  Step 7: Substitute the values into the Kpc expression

= 1.83

Since the value of Kpc is larger than 1, methylamine is more soluble in the organic solvent than
in water

Factors Affecting the Partition Coefficient

 The partition coefficient (Kpc) depends on the solubilities of the solute in the two solvents

 The degree of solubility of a solute is determined by how strong the intermolecular
bonds between solute and solvent  are
 The strength of these intermolecular bonds, in turn, depends on the polarity of
the solute and solvent molecules
 For example, ammonia is more soluble in water than in an organic solvent such as carbon
tetrachloride (CCl4)
o Ammonia and water are both polar molecules that form hydrogen bonds with
each other
o Ammonia forms permanent dipole-induced dipole forces with the non-polar
CCl4 molecules
o Since these forces are much weaker than hydrogen bonding, ammonia is less
soluble in CCl4
 When Kpc is < 1 the solute is more soluble in water than the organic solvent
 When Kpc is > 1 the solute is more soluble in the organic solvent than the water

5.6.1 Basics of Kinetics

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Kinetics: Basics

 The rate of reaction refers to the change in the amount or concentration of a reactant or

product per unit time and can be found by:
 Measuring the decrease in the concentration of a reactant OR
 Measuring the increase in the concentration of a product over time
o The units of rate of reaction are mol dm-3 s-1
Rate equation

 The thermal decomposition of calcium carbonate (CaCO3) will be used as an example to

study the rate of reaction

CaCO3 (s) → CaO (s) + CO2 (g)

 The rate of reaction at different concentrations of CaCO3 is measured and tabulated

Rate of reactions table

  A directly proportional relationship between the rate of the reaction
and concentration of CaCO3 is observed when a graph is plotted

Rate of thermal decomposition of CaCO3 over the concentration of CaCO3

 The rate of reaction for the thermal decomposition of CaCO3 can also be written as:

Rate of reaction = k x [CaCO3]

 The proportionality constant k is the gradient of the graph and is also called the rate
constant
 The rate equation is the overall expression for a particular reaction without the ‘x’ sign

Rate of reaction = k [CaCO3]

 Rate equations can only be determined experimentally and cannot be found from

the stoichiometric equation

Rate of reaction = k [A]m [B]n

[A] and [B] = concentrations of reactants

m and n = orders of the reaction

 For example, the rate equation for the formation of nitrogen gas (N2) from nitrogen
oxide (NO) and hydrogen (H2) is rate = k [NO]2 [H2]

2NO (g) + 2H2 (g) → N2 (g) + 2H2O (g)

rate = k [NO]2 [H2]

 As mentioned before, the rate equation of the reaction above cannot be deduced from the
stoichiometric equation but can only experimentally be determined by:
o Changing the concentration of NO and determining how it affects the rate while
keeping [H2] constant
o This shows that the rate is proportional to the square of [NO]

Rate = k1 [NO]2

 Then, changing the [H2] and determining how it affects the rate while keeping [NO]
constant
 This shows that the rate is proportional to [H2]

Rate = k2 [H2]
  Combining the two equations gives the overall rate equation (where k = k1 + k2)

Rate = k [NO]2 [H2]

Order of reaction

 The order of reaction shows how the concentration of a reactant affects the rate of

reaction
o It is the power to which the concentration of that reactant is raised in the rate
equation
o The order of reaction can be 0, 1,2 or 3
o When the order of reaction of a reactant is 0, its concentration is ignored
 The overall order of reaction is the sum of the powers of the reactants in a rate equation
 For example, in the following rate equation, the reaction is:

Rate = k [NO2]2[H2]


o Second-order with respect to NO
o First-order with respect to H2
o Third-order overall (2 + 1)

Half-life

 The half-life (t1/2) is the time taken for the concentration of a limiting reactant to become
half of its initial value

Rate-determining step & intermediates

 The rate-determining step is the slowest step in a reaction

 If a reactant appears in the rate-determining step, then the concentration of that reactant
will also appear in the rate equation
 For example, the rate equation for the reaction below is rate = k [CH3Br] [OH-]

CH3Br + OH- → CH3OH + Br-


o This suggests that both CH3Br and OH- take part in the slow rate-determining
step
 This reaction is, therefore, a bimolecular reaction
o Unimolecular: one species involved in the rate-determining step
o Bimolecular: two species involved in the rate-determining step
 The intermediate is derived from substances that react together to form it in the rate-
determining step
o For example, for the reaction above the intermediate would consist of CH3Br and
OH-
The intermediate is formed from the species that are involved in the rate-determining step (and
thus appear in the rate equation)

5.6.2 Kinetics Calculations

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Kinetics: Calculations
Order of reaction

 The order of reaction shows how the concentration of a reactant affects the rate of

reaction

Rate = k [A]m [B]n

 When m or n is zero = the concentration of the reactants does not affect the rate
 When the order of reaction (m or n) of a reactant is 0, its concentration is ignored
 The overall order of reaction is the sum of the powers of the reactants in a rate equation
 For example, in the reaction below, the overall order of reaction is 2 (1 + 1)

Rate = k [NO2] [Cl2]

Order of reaction from concentration-time graphs

 In a zero-order the concentration of the reactant is inversely proportional to time

o This means that the concentration of the reactant decreases with increasing
time
o The graph is a straight line going down
 Concentration-time graphs of a zero-order reaction

 In a first-order reaction the concentration of the reactant decreases with time

o The graph is a curve going downwards and eventually plateaus
 Concentration-time graphs of a first-order reaction

 In a second-order reaction the concentration of the reactant decreases more steeply with

time
o The concentration of reactant decreases more with increasing time compared to in
a first-order reaction
o The graph is a steeper curve going downwards
 Concentration-time graphs of a second-order reaction

Order of reaction from initial rate

 The progress of the reaction can be followed by measuring the initial rates of the

reaction using various initial concentrations of each reactant
 These rates can then be plotted against time in a rate-time graph
 In a zero-order reaction the rate doesn’t depend on the concentration of the reactant
o The rate of the reaction therefore remains constant throughout the reaction
o The graph is a horizontal line
o The rate equation is rate = k
 Rate-time graph of a zero-order reaction

 In a first-order reaction the rate is directly proportional to the concentration of a reactant

o The rate of the reaction decreases as the concentration of the reactant decreases
when it gets used up during the reaction
o The graph is a straight line
o The rate equation is rate = k [A]
 Rate-time graph of a first-order reaction

 In a second-order reaction, the rate is directly proportional to the square of concentration

of a reactant
o The rate of the reaction decreases more as the concentration of the reactant
decreases when it gets used up during the reaction
o The graph is a curved line
o The rate equation is rate = k [A]2
 Rate-time graphs of a second-order reaction

Order of reaction from half-life

 The order of a reaction can also be deduced from its half-life (t1/2 )

 For a zero-order reaction the successive half-lives decrease with time
o This means that it would take less time for the concentration of reactant to halve
as the reaction progresses
 The half-life of a first-order reaction remains constant throughout the reaction
 o The amount of time required for the concentration of reactants to halve will be the
same during the entire reaction
 For a second-order reaction, the half-life increases with time
o This means that as the reaction is taking place, it takes more time for the
concentration of reactants to halve

Half-lives of zero, first and second-order reactions

Calculating the initial rate

 The initial rate can be calculated by using the initial concentrations of the reactants in

the rate equation
 For example, in the reaction of bromomethane (CH3Br) with hydroxide (OH-) ions to
form methanol (CH3OH) the reaction equation and rate are as follows:

CH3Br + OH- → CH3Br + Br- (aq)

Rate = k [CH3Br] [OH-]

Where k = 1.75 x 10-2 dm-2 mol-1 s-1

  If the initial concentrations of CH3Br and OH- are 0.0200 and 0.0100 mol dm-
3
 respectively, the initial rate of reaction is:

Rate = k [CH3Br] [OH-]

Initial rate = 1.75 x 10-2 x (0.0200) x (0.0100)

Initial rate = 3.50 x 10-6 mol dm-3 s-1

5.6.3 Half-Life
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First Order Reaction Half-life

 The half-life of a first-order reaction is independent of the concentration of reactants

o This means that despite the concentrations of the reactants decreasing during
the reaction
o The amount of time taken for the concentrations of the reactants to halve will
remain the same throughout the reaction
o The graph is a straight line going downwards
 The rearrangement of the methyl group (CH3) in ethanenitrile (CH3CN) is an example
of a first-order reaction with rate equation rate = k [CH3CN]

CH3CN (g) → CH3NC (g)

Rearrangement of the CH3 group in CH3CN

 Experimental data of the changes in concentration over time suggests that the half-life is
constant
o Even if the half-lives are slightly different from each other, they can still be
considered to remain constant
 This means that no matter what the original concentration of the CH3CN is, the half-life
will always be around 10.0 minutes
Half-life table
In a first-order reaction, the time taken for the concentration to halve remains constant
Worked Example: Using the half-life of first-order reactions in
calculations
Answer

 Step 1: Plot the concentration-time graph using appropriate scales and labels for the axis
  Step 2: Find the first and second half-lives by determining when the concentrations halve
using the graph

Step 2 table

 Step 3: Determine the reaction order

It is s a first-order reaction as the successive half-lives remain reasonably constant

(around 450 seconds) throughout the reaction

5.6.4 Rate Constant Calculations

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Calculating the Rate Constant

 The rate constant (k) of a reaction can be calculated using:

o The initial rates and the rate equation
o The half-life

Calculating the rate constant from the initial rate

  The reaction of calcium carbonate (CaCO3) with chloride (Cl-) ions to form calcium
chloride (CaCl2) will be used as an example to calculate the rate constant from the initial
rate and initial concentrations
 The reaction and rate equation are as follows:

CaCO3 (s) + 2Cl- (aq) + 2H+ (aq) → CaCl2 (aq) + CO2 (g) + H2O (l)

Rate = k [CaCO3] [Cl-]

 The progress of the reaction can be followed by measuring the initial rates of the

reaction using various initial concentrations of each reactant

Experimental results of concentrations & initial rates table

 To find the rate constant (k):

o Rearrange the rate equation to find k
  Substitute the values of one of the experiments to find k (for example measurement 1)

= 1.40 x 10-2 dm3 mol-1 s-1

 The values of measurement 2 or 3 could also have been used to find k (they all give the
same result of 1.40 x 10-2 dm3 mol-1 s-1)

Calculating the rate constant from the half-life

 The rate constant (k) can also be calculated from the half-life of a reaction
 You are only expected to deduce k from the half-life of a first-order reaction as the
calculations for second and zero-order reactions are more complicated
 For a first-order reaction, the half-life is related to the rate constant by the following
expression:

 Rearranging the equation to find k gives:

 So, for a first-order reaction such as

the methyl (CH3) rearrangement in ethanenitrile (CH3CN) with a half-life of 10.0
minutes the rate constant is:

= 1.16 x 10-3 dm3 mol-1 s-1

5.6.5 Multi-Step Reactions

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Kinetics of Multi-Step Reactions

 The reaction mechanism of a reaction describes how many steps are involved in

the making and breaking of bonds during a chemical reaction
 It is the slowest step in a reaction and includes the reactants that have an impact on the
reaction rate when their concentrations are changed
o Therefore, ll reactants that therefore appear in the rate equation will also appear
in the rate-determining step
o This means that reactants that have a zero-order and intermediates will not be
present in the rate-determining step

Predicting the reaction mechanism

 The overall reaction equation and rate equation can be used to predict a possible

reaction mechanism of a reaction
 For example, nitrogen dioxide (NO2) and carbon monoxide (CO) react to form nitrogen
monoxide (NO) and carbon dioxide (CO2)
 The overall reaction equation is:

NO2 (g) + CO (g) → NO (g) + CO2 (g)

 The rate equation is:

Rate = k [NO2]2

 From the rate equation it can be concluded that the reaction is zero order with respect to
CO (g) and second order with respect to NO2 (g)
 This means that there are two molecules of NO2 (g) involved in the rate-determining
step
 A possible reaction mechanism could therefore be:

 Step 1:

2NO2 (g) → NO (g) + NO3 (g)     slow (rate-determining step)

 Step 2:

NO3 (g) + CO (g) → NO2 (g) + CO2 (g)     fast

 Overall:
2NO2 (g) + NO3 (g) + CO (g) → NO (g) + NO3 (g) + NO2 (g) + CO2 (g)

=     NO2 (g) + CO (g) → NO (g) + CO2 (g)

Predicting the reaction order & deducing the rate equation

 The order of a reactant and thus the rate equation can be deduced from a reaction
mechanism given that the rate-determining step is known
 For example, the reaction of nitrogen oxide (NO) with hydrogen (H2) to form nitrogen
(N2) and water

2NO (g) + 2H2 (g) → N2 (g) + 2H2O (l)

 The reaction mechanism for this reaction is:

 Step 1:

NO (g) + NO (g) → N2O2 (g)     fast

 Step 2:

N2O2 (g) + H2 (g) → H2O (l) + N2O (g)     slow (rate-determining step)

 Step 3:

N2O (g) + H2 (g) → N2 (g) + H2O (l)     fast

 The second step in this reaction mechanism is the rate-determining step

 The rate-determining step consists of:
o N2O2 which is formed from the reaction of two NO molecules
o One H2 molecule
 The reaction is, therefore, second order with respect to NO and first order with respect
to H2
 So, the rate equation becomes:

Rate = k [NO]2 [H2]

 The reaction is, therefore, third order overall

Identifying the rate-determining step

 The rate-determining step can be identified from a rate equation given that the reaction
mechanism is known
 For example, propane (CH3CH2CH3) undergoes bromination under alkaline solutions
  The overall reaction is:

CH3CH2CH3 + Br2 + OH- → CH3CH2CH2Br + H2O + Br-

 The reaction mechanism is:

Reaction mechanism of the bromination of propane under alkaline conditions

 The rate equation is:

Rate = k [CH3CH2CH3] [OH-]

 From the rate equation, it can be deduced that only CH3COCH3 and OH- are involved in
the rate-determining step and not bromine (Br2)
 Since only in step 1 of the reaction mechanism are CH3COCH3 and OH- involved,
the rate-determining step is step 1 is the case for step 1 of the reaction mechanism

Identifying intermediates & catalyst

  When a rate equation includes a species that is not part of the chemical reaction equation
then this species is a catalyst
 For example, the halogenation of butanone under acidic conditions
 The reaction mechanism is:

 The reaction mechanism is:

 
 Reaction mechanism of the halogenation of butanone under acidic conditions

 The rate equation is:

Rate = k [CH3CH2COCH3] [H+]

 The H+ is not present in the chemical reaction equation but does appear in the rate

equation
o H+ must therefore be a catalyst
 Furthermore, the rate equation suggest that CH3CH2COCH3 and H+ must be involved in
the rate-determining (slowest) step
  The CH3CH2COCH3 and H+ appear in the rate-determining step in the form of
an intermediate (which is a combination of the two species)

Intermediate is formed in the rate-determining step from the reaction of CH3CH2COCH3 and

H+

5.6.6 Factors affecting Rate Constant

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Effect of Temperature on the Rate Constant

 At higher temperatures, a greater proportion of molecules have energy greater than than
the activation energy
 Since the rate constant and rate of reaction is directly proportional to the fraction of
molecules with energy equal or greater than the activation energy, then at higher
temperatures:
o The rate constant increases
o The rate of reaction increases
 The relationship between the rate constant and the temperature is given by the following
equation:

ln k = natural logarithm of the rate constant

A = constant related to the collision frequency and orientation of the molecules

Ea = activation energy (joules, J)

R = gas constant (8.31 J K-1 mol-1)

T = temperature (kelvin, K)

 A varies only a little bit with temperature, it can be considered a constant

 Ea and R are also constants

 The equation shows that an increase in temperature (higher value of T) gives
a greater value of ln k (and therefore a higher value of k)
 Since the rate of the reaction depends on the rate constant (k) an increase in k also
means an increased rate of reaction
 The graph of ln k over 1/T is a straight line with gradient -Ea/R

Exam Tip
You are not required to learn this equation however it is helpful in understanding the effects of
temperature on the rate constant.
5.6.7 Homogeneous & Heterogeneous
Catalysts
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Homogeneous & Heterogeneous Catalysis

 Catalysts increase the rate of reaction by providing an alternative pathway which has a

lower activation energy
 Catalysts can be either homogeneous or heterogeneous
 Homogeneous catalysts are those that are in the same phase as the reaction mixture
 For example, in the esterification of ethanoic acid (CH3COOH) with ethanol (CH3CH2OH)
to form ethyl ethanoate (CH3COOCH2CH3) under acidic conditions

 The H+ is a homogeneous catalyst as like the reactants and product it is in

the aqueous phase

 Heterogeneous catalysts are those that are in a different phase to the rest of the reaction
mixture
 For example, in the Born-Haber process to form ammonia (NH3) from nitrogen (N2) and
hydrogen (H2) an iron (Fe) catalyst is used

 The Fe catalyst is a heterogeneous catalyst as it is in the solid phase whereas the reactants

and products are all in the gas phase

Heterogeneous Catalysis

 In heterogeneous catalysis, the molecules react at the surface of a solid catalyst

 The mode of action of a heterogeneous catalyst consists of the following steps:
 Adsorption (or chemisorption) of the reactants on the catalyst surface
 o The reactants diffuse to the surface of the catalyst
o The reactant is physically adsorbed onto the surface by weak forces
o The reactant is chemically adsorbed onto the surface by stronger bonds
o Chemisorption causes bond weakening between the atoms of the reactants
 Desorption of the products
o The bonds between the products and catalyst weaken so much that the products
break away from the surface
 For example, the adsorption of hydrogen molecules onto a palladium (Pd) surface

The reactants are adsorbed on the catalyst surface causing bond weakening and eventually
desorption of the products

Iron in the Haber process

 In the Haber process ammonia (NH3) is produced from nitrogen (N2) and hydrogen (H2)

 An iron catalyst is used which speeds up the reaction by bringing the reactants close
together on the metal surface
 This increases their likelihood to react with each other
 The mode of action of the iron catalyst is as follows:
o Diffusion of the nitrogen and hydrogen gas to the iron surface
o Adsorption of the reactant molecules onto the iron surface by forming bonds
between the iron and reactant atoms
 These bonds are so strong that they weaken the covalent bonds between
the nitrogen atoms in N2 and hydrogen atoms in H2
 But they are weak enough to break when the catalysis has been completed
o The reaction takes place between the adsorbed nitrogen and hydrogen atoms
which react with each other on the iron surface to form NH3
o Desorption occurs when the bonds between the NH3 and iron surface are
weakened and eventually broken
o The formed NH3 diffuses away from the iron surface
 Iron brings the nitrogen and hydrogen closer together so that they can react and hence
increases the rate of reaction

Heterogeneous catalyst in catalytic converters

 Heterogeneous catalysts are also used in the catalytic removal of oxides of nitrogen

from the exhaust gases of car engines
 The catalysts speed up the conversion of:
o Nitrogen oxides (NOy) into harmless nitrogen gas (N2)
o Carbon monoxide (CO) into carbon dioxide (CO2)
 The catalytic converter has a honeycomb structure containing small beads coated
with platinum, palladium, or rhodium metals which act as heterogeneous catalysts
 The mode of action of the catalysts is as following:
o Adsorption of the nitrogen oxides and CO onto the catalyst surface
o The weakening of the covalent bonds within nitrogen oxides and CO
o Formation of new bonds between:
 Adjacent nitrogen atoms to form N2 molecules
 CO and oxygen atoms to form CO2 molecules
o Desorption of N2 and CO2 molecules which eventually diffuse away from the
metal surface
 The metals in catalytic converters speed up the conversion of nitrogen oxides and CO into
N2 and CO2 respectively

Homogeneous Catalysis

 Homogeneous catalysis often involves redox reactions in which the ions involved in

catalysis undergo changes in their oxidation number
o As ions of transition metals can change oxidation number they are often good
catalysts
 Homogeneous catalysts are used in one step and are reformed in a later step

The iodine-peroxydisulfate reaction

 This is a very slow reaction in which the peroxydisulfate (S2,O82- )

ions oxidise the iodide to iodine

S2O82- (aq) + 2I- (aq) → 2SO42- (aq) + I2 (aq)

 Since both the S2O82- and I- ions have a negative charge, it will require a lot of energy for
the ions to overcome the repulsive forces and collide with each other
 Therefore, Fe3+ (aq) ions are used as a homogeneous catalyst
 The catalysis involves two redox reactions:
o First, Fe3+ ions are reduced to Fe2+ by  I-

2Fe3+ (aq) + 2I- (aq) → 2Fe2+ (aq) + I2 (aq)


o Then, Fe2+ is oxidized back to Fe3+ by S2O82-
 2Fe2+ (aq) + S2O82- (aq) → 2Fe3+ (aq) + 2SO42-  (aq)

 By reacting the reactants with a positively charged Fe ion, there are no repulsive forces,
and the activation energy is significantly lowered
 The order of the two reactions does not matter
o So, Fe2+ can be first oxidised to Fe3+ followed by the reduction of Fe3+ to Fe2+

The catalysed reaction has two energy ‘humps’ because it is a two-stage reaction

Nitrogen oxides & acid rain

 As fossil fuels contain sulfur, burning the fuels will release sulfur dioxide which oxidises
in air to sulfur trioxide, and then dilute sulfuric acid (H2SO4) is formed by reaction with
water. The result is acidification of rain:

SO3(g) + H2O(l) → H2SO4(aq)

 Nitrogen oxides can act as catalysts in the formation of acid rain by catalysing the
oxidation of SO2 to SO3

NO2(g) + SO2(g) → SO3(g) + NO(g)

 The formed NO gets oxidised to regenerate NO2

NO(g) + ½ O2(g) → NO2(g)

 The regenerated NO2 molecule can again oxidise another SO2 molecule to SO3 which will
react with rainwater to form H2SO4 and so on