Reactivity 3.

2 HL
Answers
IB CHEMISTRY HL
Reactivity 3.2.12
Understandings:
• The hydrogen half-cell H2(g) ⇌ 2H+(aq) + 2e– is assigned a standard electrode
potential of zero by convention. It is used in the measurement of standard
electrode potentials, E⦵.
Learning outcomes:
• Interpret standard electrode potential data in terms of ease of oxidation/reduction.
Additional notes:
• Standard electrode potentials are given in the data booklet.

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Hydrogen half-cell
• The hydrogen half-cell, also known as the standard hydrogen electrode (SHE), is
a reference electrode used to measure the standard electrode potentials, E⦵, of
other half-cells.
• The hydrogen half-cell is assigned a standard electrode potential (E⦵) of 0 V.
• The conditions of the hydrogen half-cell are:
▪ Hydrogen gas (H2) at a pressure of 100 kPa
▪ A temperature of 298 K
▪ A 1.0 mol dm-3 of H+ ions
▪ An inert platinum electrode

• Depending on which half-cell is connected to the hydrogen half-cell, hydrogen

ions are reduced to form hydrogen gas, or hydrogen gas is oxidised to form
hydrogen ions.
2H+(aq) + 2e– ⇌ H2(g) H2(g) ⇌ 2H+(aq) + 2e–

Standard electrode potential (E⦵)

• The standard electrode potential, E⦵, is the electrode potential (in V) of a half-cell
measured under standard conditions relative to the hydrogen half-cell.
• Standard electrode potential values can be found in section 19 of the data booklet.

Standard conditions used when comparing half-cells:

• Solutions with a concentration of 1.00 mol dm–3
• Gases at a pressure of 100 kPa.
• All substances must be pure.
• Temperature of 298 K
• If the half-cell does not include a solid metal, platinum is used as the electrode.

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In the diagram shown below, the hydrogen half-cell is connected to a zinc half-cell.
• The voltage produced is 0.76 V.
• The electrons flow from the zinc half-cell to the hydrogen half-cell.
• When a half-cell above hydrogen in section 19 of the data booklet is connected to
the hydrogen half-cell, electrons flow to the hydrogen half-cell and the standard
electrode potential value is given a negative value.

• The standard electrode potential, E⦵, of the zinc half-cell is -0.76 V.

In the diagram below, the hydrogen half-cell is connected to a copper half-cell.

• The voltage produced is 0.34 V.
• The electrons flow from the hydrogen half-cell to the copper half-cell.
• When a half-cell below hydrogen in section 19 of the data booklet is connected to
the hydrogen half-cell, electrons flow from the hydrogen half-cell and the standard
electrode potential value is positive.

• The standard electrode potential, E⦵, of the copper half-cell is +0.34 V.

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Reactivity 3.2.13
Understandings:
• Standard cell potential, E⦵, can be calculated from standard potentials. E⦵ has a
positive value for a spontaneous reaction.
Learning outcomes:
• Predict whether a reaction is spontaneous in the forward or reverse direction
from E⦵.

Calculating standard cell potential (E⦵cell)

• The following equation is used to calculate the cell potential (E⦵cell).
E⦵cell = E⦵red – E⦵ox or E⦵cell = E⦵cathode – E⦵anode

• The standard electrode potential values are the reduction potentials and must be
used as given in section 19 of the data booklet.
• E⦵ values are intensive quantities and are not multiplied according to the
stoichiometry of the equation.
• A reaction with a positive E⦵cell value is spontaneous as written and the reverse
reaction is non-spontaneous.
• A reaction with a negative E⦵cell value is non-spontaneous as written and the
reverse reaction is spontaneous.

Example: Calculate the E⦵cell for the following reaction. Comment on the spontaneity of
the reaction.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Zn2+(aq) + 2e– ⇌ Zn(s) E⦵ = –0.76 V
Cu2+(aq) + 2e– ⇌ Cu(s) E⦵ = +0.34 V
E⦵cell = 0.34 – (– 0.76) = +1.10 V

Exercises:
1) Calculate the E⦵cell for the following reaction. Comment on the spontaneity of the
reaction.
Mg(s) + Fe2+(aq) → Mg2+(aq) + Fe(s)
Mg2+(aq) + 2e– ⇌ Mg(s) E⦵ = –2.37 V
Fe2+(aq) + 2e– ⇌ Fe(s) E⦵ = –0.45 V

E⦵cell = –0.45 – (–2.37) = +1.92 V

The E⦵cell value is positive therefore the reaction is spontaneous as written.

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 2) Calculate the E⦵cell for the following reaction. Comment on the spontaneity of the
reaction.
Cr2+(aq) + Cu2+(aq) → Cr3+(aq) + Cu+(aq)

Cr3+(aq) + e– ⇌ Cr2+(aq) E⦵ = –0.41 V

Cu2+(aq) + e– ⇌ Cu+(aq) E⦵ = +0.15 V

E⦵cell = Ered – Eox

E⦵cell = +0.15 – (–0.41) = +0.56 V
The E⦵cell value is positive therefore the reaction is spontaneous as written.

3) Calculate the standard cell potential, E⦵cell, of a voltaic cell consisting of a nickel
half-cell and a silver half-cell.

Ni2+(aq) + 2e– ⇌ Ni(s) E⦵ = –0.26 V

Ag+(aq) + e– ⇌ Ag(s) E⦵ = +0.80 V

E⦵cell = +0.80 – (–0.26) = +1.06 V

4) Calculate the standard cell potential, E⦵cell, of a voltaic cell consisting of an

aluminum half-cell and an iron half-cell.

Al3+(aq) + 3e– ⇌ Al(s) E⦵ = –1.66 V

Fe2+(aq) + 2e– ⇌ Fe(s) E⦵ = –0.44 V

E⦵cell = –0.44 – (–1.66) = +1.22 V

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Reactivity 3.2.14
Understandings:
• The equation ΔG⦵ = −nFE⦵ shows the relationship between standard cell change
in Gibbs energy and standard electrode potential for a reaction.
Learning outcomes:
• Determine the value for ΔG⦵ from E⦵ data.
Additional notes:
• The equation and the value of F in C mol–1 are given in the data booklet.
Linking questions:
• Reactivity 1.4 How can thermodynamic data also be used to predict the
spontaneity of a reaction?

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Relationship between E⦵cell and ΔG⦵
• The following equation can be found in section 1 of the data booklet:
ΔG⦵ = –nFE⦵cell
• n is the amount (in mol) of electrons transferred in the reaction
• F is the Faraday constant (96500 C mol–1).
• For a spontaneous reaction, the ΔG⦵ is negative and the E⦵cell is positive.
• For a non-spontaneous reaction, the ΔG⦵ is positive and the E⦵cell is negative.
• The relationship between the E⦵cell and ΔG⦵ is summarised in the table below.

ΔG⦵ E⦵cell Spontaneity

Negative Positive Spontaneous
Positive Negative Non-spontaneous
Zero Zero Reaction is at equilibrium

Exercises: Calculate the ΔG⦵ for the following reactions. Comment on the spontaneity
of the reaction in each case.

1) Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) E⦵cell = +1.10 V

ΔG⦵ = –2 × 96500 × 1.10

ΔG⦵ = –212 kJ mol-1
ΔG⦵ is negative therefore reaction is spontaneous as written.

2) Ni2+(aq) + Mn(s) → Ni(s) + Mn2+(aq) E⦵cell = –0.93 V

ΔG⦵ = –2 × 96500 × –0.93

ΔG⦵ = +179 kJ mol-1
ΔG⦵ is positive therefore reaction is non-spontaneous as written.

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Reactivity 3.2.15
Understandings:
• During electrolysis of aqueous solutions, competing reactions can occur at the
anode and cathode, including the oxidation and reduction of water.
Learning outcomes:
• Deduce from standard electrode potentials the products of the electrolysis of
aqueous solutions.
Additional notes:
• Electrolytic processes should include the electrolysis of water and of aqueous
solutions.

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Electrolysis of aqueous solutions
• When aqueous solutions are electrolysed, water can be oxidised at the anode or
reduced at the cathode.

At the cathode (reduction): 2H2O(l) + 2e– → H2(g) + 2OH–(aq)

At the anode (oxidation): 2H2O(l) → 4H+(aq) + O2(g) + 4e–

Electrolysis of water (H2O)

• Pure water is a poor conductor of electricity, therefore NaOH or H2SO4 is added to
increase its conductivity.

At the cathode:
Na+(aq) + e– → Na(s) E⦵ = –2.71 V
2H2O(l) + 2e– → H2(g) + 2OH–(aq) E⦵ = –0.83 V
• H2O is reduced instead of Na+ ions because H2O is a stronger oxidising agent /
Na+ is a weaker oxidising agent.

At the anode:
4OH–(aq) → 2H2O(l) + O2(g) + 4e– E⦵ = –0.40 V
2H2O(l) → 4H+(aq) + O2(g) + 4e– E⦵ = –1.23 V
• Both reactions result in the formation of O2 at the anode.

Overall equation:
2H2O(l) → 2H2(g) + O2(g)

Observed changes at the electrodes:

• A colorless gas is evolved at the anode and cathode.
• The ratio of H2 to O2 is 2:1
• The pH at the anode decreases (increase in [H+]) and the pH at the cathode
increases (increase in [OH–]).

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Electrolysis of aqueous sodium chloride, NaCl(aq)
• The products of the electrolysis of aqueous solution that contain chloride ions
depend on the concentration of the solution.

At the cathode:
Na+(aq) + e– → Na(s) E⦵ = –2.71 V
2H2O(l) + 2e– → H2(g) + 2OH–(aq) E⦵ = –0.83 V
• H2O is reduced instead of Na+ ions because H2O is a stronger oxidising agent /
Na+ is a weaker oxidising agent.

At the anode:
2H2O(l) → 4H+(aq) + O2(g) + 4e– E⦵ = –1.23 V
2Cl–(aq) → Cl2(g) + 2e– E⦵ = –1.36 V
• At low concentrations – dilute NaCl(aq) – O2(g) is produced.
• At high concentrations – concentrated NaCl(aq) – Cl2(g) is produced.

Electrolysis of aqueous copper(II) sulfate, CuSO4(aq)

Inert (graphite electrodes)

At the cathode:
2H2O(l) + 2e– → H2(g) + 2OH–(aq) E⦵ = –0.83 V
Cu2+(aq) + 2e– → Cu(s) E⦵ = +0.34 V
At the anode:
2H2O(l) → 4H+(aq) + O2(g) + 4e– E⦵ = –1.23 V
Copper electrodes

At the cathode:
Cu2+(aq) + 2e– → Cu(s) E⦵ = +0.34 V
At the anode:
Cu(s) → Cu2+(aq) + 2e– E⦵ = –0.34 V

Observed changes at electrodes with graphite electrodes:

• Pinky-brown colour as copper is deposited on the cathode.
• The blue color is lost because of discharge of Cu2+ ions.
Observed changes at electrodes with copper electrodes:
• Pinky-brown color develops as copper is deposited on the cathode.
• Copper anode loses mass.
• No change in pH.
• No change in blue color because Cu2+ ions are formed and removed from the
solution so the concentration remains constant.
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Exercises:

1) Predict the products at the anode and cathode when the following aqueous
solutions are electrolysed using platinum electrodes.
(a) Dilute sodium iodide solution
anode: O2(g) cathode: H2(g)

(b) Copper(II) nitrate solution

anode: O2(g) cathode: Cu(s)

(c) Concentrated magnesium chloride solution

anode: Cl2(g) cathode: H2(g)

(d) Sodium hydroxide solution

anode: O2(g) cathode: H2(g)

2) Write half equations for the reactions that occur at the electrodes when copper(II)
sulfate solution is electrolysed:
(a) Using copper electrodes.
anode: Cu(s) → Cu2+(aq) + 2e-
cathode: Cu2+(aq) + 2e- → Cu(s)

(b) Using platinum electrodes.

anode: 2H2O(l) → O2(g) + 4H+(aq) + 4e–
cathode: Cu2+(aq) + 2e– → Cu(s)

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Reactivity 3.2.16
Understandings:
• Electroplating involves the electrolytic coating of an object with a metallic thin
layer.
Learning outcomes:
• Deduce equations for the electrode reactions during electroplating.

Electroplating
• Electroplating involves the electrolytic coating of an object with a thin layer of
metal.
• The object to be coated is the cathode, the metal coated is the anode in a solution
of aqueous metal ions.
• The electrolyte is an aqueous solution of the same ions as the anode material.

Anode: Ag(s) → Ag+(aq) + e–

Cathode: Ag+(aq) + e– → Ag(s)

Factors that affect the amount of product in an electrolysis reaction

The factors that affect the amount of product formed in an electrolysis reaction are:
• duration of the electrolysis
• current supplied
• charge on the ion

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