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CIE A Level Chemistry Your notes

5.4 Electrochemistry Calculations & Applications (A

Level Only)
Contents
5.4.1 Electrolysis: Calculations
5.4.2 Standard Cell Potential: Calculations, Electron Flow & Feasibility
5.4.3 Electrochemical Series & Redox Equations
5.4.4 Non-Standard Conditions
5.4.5 Nernst Equation
5.4.6 Standard Electrode Potentials: Free Energy Change

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5.4.1 Electrolysis: Calculations

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Calculations in Electrolysis
Faraday’s constant can be used to calculate:
The mass of a substance deposited at an electrode
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:
Write the half-equation at the electrode
Determine the number of coulombs needed to form one mole of substance at the specific
electrode using Faraday’s constant
Calculate the charge transferred during electrolysis
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:

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F = 2 x 96 500
F = 193 000 C mol-1 Your notes
Step 3: Calculate the charge transferred during the electrolysis
Q=Ixt
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:
Write the half-equation at the electrode
Determine the number of coulombs needed to form one mole of substance at the specific
electrode using Faraday’s constant
Calculate the charge transferred during electrolysis
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

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Your notes

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=Ixt
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

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Your notes

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

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F = 96 500 C
So, for two moles of electrons, the number of coulombs needed is: Your notes
F = 2 x 96 500
F = 193 000 C
Step 3: Calculate the charge transferred during the electrolysis
Q=Ixt
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

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5.4.2 Standard Cell Potential: Calculations, Electron Flow &

Feasibility Your notes

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
The half-cell with the more positive Eꝋ value will be the positive pole
The positive electrode or cathode is the one which most favours reduction
The half-cell with the less positive Eꝋ value will be the negative pole
The negative electrode or anode is the one which most favours oxidation
Worked example: Calculating the standard cell potential

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Your notes

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
To show the processes taking place in the cell to further explain

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Your notes

Ionic equations in the cell

Exam Tip
Students often confuse the redox process that take place in voltaic cells and electrolytic cells.
An easy way to remember is the phrase RED CATS: REDuction takes place at the CAThode.
OR
AN OX. OXidation takes place at the ANode

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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:
The species is easily reduced
The species is a better oxidising agent
Less positive (more negative) Eꝋ values indicate that:
The species is easily oxidised
The species is a better reducing agent

Example of an electrochemical series in which the equilibria are arranged in order of decreasing Eꝋ
values

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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

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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:
Your notes
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

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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
RT Θ ⎣ o xidi s e d s p e cie s ⎥⎦
⎡⎢ ⎤
E = E + ln ⎡
zF ⎢⎣r e d u c e d s p e cie s ⎤⎥⎦
E = electrode potential under nonstandard conditions
Eθ = 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
0 . 059
Θ
⎡⎢ o xidi s e d s p e cie s ⎤⎥
E = E + log 10
⎣ ⎦
z ⎡⎢r e d u c e d s p e cie s ⎤⎥
⎣ ⎦
At standard temperature, R, T and F are constant
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

Worked example: Calculating the electrode potential of a Fe3+/Fe2+ half-cell

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Your notes

Answer
From the question, the concentrations of ions for the Fe3+ / Fe2+ half-cell are as follows:
[Fe3+] = 0.034 mol dm-3
[Fe2+] = 0.64 mol dm-3
EΘ = + 0.77 V
The oxidised species is Fe3+ as it has a higher oxidation number (+3)
The reduced species is Fe2+ as it has a lower oxidation number (+2)
z is 1 as only one electron is transferred in this reaction
The Nernst equation for this half-reaction is, therefore:
Θ 0 . 059 ⎡⎢ oxidis e d s p e cie s ⎤⎥
E = E +
⎣ ⎦
log 10 ⎡
z ⎢⎣r e d uc e d s p e cie s ⎤⎥⎦

0 . 059 ⎡⎢ 0 . 034 ⎤⎥
E = 0 . 77 +
⎣ ⎦
log 10 ⎡
1 ⎢⎣ 0 . 64 ⎤⎥⎦
E = (+0.77) + (-0.075)
E = +0.69 V
Worked example: Calculating the electrode potential of a Cu2+/Cu half-cell

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Your notes

Answer
From the question, the concentrations of ions for the Fe3+ / Fe2+ half-cell are as follows:
[Cu2+] = 0.0010 mol dm-3
EΘ = + 0.34 V
The oxidised species is Cu2+ as it has a higher oxidation number (+2)
The reduced species is Cu as it has a lower oxidation number (0)
Cu is solid which means that it is not included in the Nernst equation
Its concentration does not change and is, therefore, fixed as 1.0
z is 2 as 2 electrons are transferred in this reaction
The Nernst equation for this half-reaction is, therefore:
Θ 0 . 059 ⎡⎢ oxidis e d s p e cie s ⎤⎥
E = E +
⎣ ⎦
log 10 ⎡
z ⎢⎣r e d uc e d s p e cie s ⎤⎥⎦

0 . 059 ⎡⎢ 0 . 0010 ⎤⎥
E = 0 . 34 +
⎣ ⎦
log 10 ⎡
2 ⎢⎣ 1 . 0 ⎤⎥⎦

E = (+ 0.34) + (– 0.089)
E = + 0.25 V

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Exam Tip
Your notes
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).

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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

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The Cu2+/Cu has a smaller Eꝋ value which means that it gets oxidised
It transfers two electrons to two Fe3+ ions Your notes
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

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