SES4UB 9: Redox Processes 11/30/2023

19.1.2 Electrolytic Cells

​Electrolysis of Aqueous Solutions
Factors Affecting Amount of Product in Electrolysis
Electroplating
Aqueous Solutions
➔ Analyzing the electrolysis of aqueous solutions is more complicated because water itself can
be oxidized or reduced
◆ At the cathode, H2O can be reduced:

2 H2O(l) + 2 e– → H2(g) + 2 OH–(aq)

◆ At the anode, H2O can be oxidized to O2:

2 H2O(l) → 4 H+(aq) + O2(g) + 4 e–

➔ Results in more than one possible redox reaction at each electrode

➔ When solute M+A- are in aqueous solution the following are possible:
◆ At the anode
● Either A- (aq) or H2O (l) can be oxidized, but not both
◆ At the cathode,
● Either M+ (aq) or H2O (l) can be reduced, but not both
➔ The outcome, which oxidation and reduction reactions occur, known as selective discharge is
determined by:
◆ The relative Eᶿ values of the ions
◆ The relative concentrations of the ions in the electrolyte
◆ The nature of the electrode

Determining the Products of Electrolysis

1. Identify all ions present in the electrolyte and determine which will migrate to which electrode:
anions to anode, and cations to cathode.

2. Where there is more than one possible reaction at each electrode, determine which will occur.
Write the half-equation for the reaction at each electrode, showing electrons released at the
anode in oxidation and taken up at the cathode in reduction.

3. Balance the electrons lost and gained at the anode and the cathode, then add the two
half-equations to write the equation for the net reaction.

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4. Consider what changes would be observed in the cell as a result of the redox processes
occurring. These may include colour changes in the electrolyte, precipitation of solid, gas
discharge, or pH changes.

Relative Eᶿ Values of Ions: Electrolysis of Water with Added NaOH (aq)

➔ Water auto-ionizes to establish the following equilibrium:

H2O(l) ↔ H+(aq) + OH-(aq)

➔ The equilibrium constant for this reaction (Kw = 1 x 10-14) at SATP is extremely small, indicating that
the reactant is highly favoured
◆ The concentration of ions in pure water are extremely low, making it a poor conductor of
electricity
➔ To electrolyse water, an ionic compound (eg. NaOH) that will not interfere with the discharge of
ions from water is added to increase the conductivity

Step 1 – Ions Present

Step 2 – Possible Reactions

Reduction at Cathode

Oxidation at Anode

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Step 3 – Overall Balanced Redox Equation

Step 4 – Observed Changes at The Electrodes

Relative Concentrations of Ions in Electrolyte: Electrolysis of NaCl (aq) (Brine)

Step 1 – Ions Present

Step 2 – Possible Reactions

Reduction at Cathode

Oxidation at Anode

However, the situation is more complicated and depends upon the concentration of Cl-(aq)

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Low [Cl-]

H2O(l) is preferentially oxidized and O2(g) is discharged at the anode

High [Cl-] (>25% by mass)

Cl-(aq) is preferentially oxidized and Cl2(g) is discharged at the anode

➔ This is what occurs during the industrial electrolysis of brine to ensure the production of Cl2(g)

Step 3 – Overall Balanced Redox Reaction (assuming saturated solution of brine)

Step 4 – Observed Changes at The Electrodes

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Nature of Electrodes: Electrolysis of CuSO4(aq) Using Inert (e.g. graphite)

Electrode

Step 1 – Ions Present

Step 2 – Possible Reactions

Reduction at Cathode

Oxidation at Anode

Step 3 – Overall Balanced Redox Equation

Step 4 – Observed Changes at The Electrodes

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Nature of Electrodes: Electrolysis of CuSO4(aq) Using Copper Electrodes

Step 1 – Ions Present

Step 2 – Possible Reactions

Reduction at Cathode

Oxidation at Anode

Step 3 – Overall Balanced Redox Equation

Step 4 – Observed Changes at The Electrodes

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Factors Affecting the Amount of Product in Electrolysis

1. Current
➔ The quantity of electric charge passed through an electrolytic cell
➔ Higher current = greater yield
2. Duration of electrolysis
➔ Longer = greater yield
3. Ion charge
➔ Na+ requires 1 mol of electrons, while Pb2+ requires 2 mols

Calculating the Amount of Product Given Current and Time

Charge = current x time

➔ The charge carried by one mole of electrons, known as a Faraday (F) is 96 500 C

Example:
a. How many grams of copper are deposited on the cathode of an electrolytic cell containing
CuCl2(aq) if a current of 2.00 A is run for 15.0 minutes?

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b. How would the amount differ if the same conditions were applied using CuCl(aq) instead?

Note: From the above example the same amount of electric charge produces twice as many moles
of Cu(s) from Cu+(aq) as from Cu2+(aq). As noted earlier the charge on the ion impacts the amount
of product formed.

Example:
1. Determine the relative quantities of electricity required to produce one mole each of Na(l) and
Pb(s) in the electrolysis of NaCl(l) and PbBr2(l).

2. If a current of 2.00 A is passed through a solution of AgNO3 for 10 minutes it is found that 0.0124
moles of Ag are formed.
a. How much would form if a current of 1.00 A is passed through the same solution for 30
minutes?

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b. What amount of Cu would form if the quantity of electricity in (a) was passed through a
solution of CuSO4?

Summary of Voltaic and Electrolytic Cells

➔ Voltaic and electrolytic cells are the reverse of each other

➔ A voltaic cell transforms _____________ energy into _____________ energy when a reaction with a
_____________ value of Ecell moves __________ equilibrium
➔ An electrolytic cell transforms _____________ energy into _____________ when an electric current
drives a reaction with a _____________ value of Ecell that moves _______________ equilibrium

Homework:
➔ Read the section on electroplating and explain how it works and list some of its uses
➔ Exercises 24-26 on p. 451
➔ Exercises 27-29 on p. 456