Key Concepts

First Law :

The mass of a substance produced by electrolysis is proportional to the quantity of

electricty used.

Example: electrolysis of liquid sodium chloride produces liquid sodium metal and
chlorine gas.

Quantity of
mass of sodium
Electricity Used Q/m
produced (m)
(Q)
28,950/6.9 Increasing the quantity of
28,950 coulombs 6.9 g
= 4196 electricity (Q) produces more
grams of sodium (m).
96,500/23.0
96,500 coulombs 23.0 g Q/m is always 4196 in this case.
= 4196
Q/m is a constant.
482,500/115.0 Q is proportional to m
482,500 coulombs 115.0 g
= 4196 that is Q m

This means that in order to produce more substance electrolytically we must use more
electricity.

Second Law:

1
The amount of electricity in coulombs required to produce 1 mole of a substance
is a simple whole number multiple of2 96 500

That is the amount of electricity (Q) in coulombs divided by 96,500 is a simple whole
number

quantity of
To produce 1 mole of
electricity required Q/96,500
underlined substance
(Q)
96,500/96,500 In each example, Q/96,500
Na+ + e- Na 96,500 coulombs
=1 is a simple whole number.
193,000/96,500
Cu2+ + 2e- Cu 193,000 coulombs If n represents that simple
=2
whole number,
Fe3+ + 3e- Fe 289,500 coulombs 289,500/96,500 and Q is the quantity of
=3 electricity in coulombs,
 then

n = Q/96,500
The quantity 96,500 is given the name the Faraday (or Faraday Constant) and the symbol
F

F is equal to the quantity of electricity carried by one mole of electrons:

F = Avogadro's Number charge on electron in coulombs
= 6.022 1023 mol-1 1.602192 10-19 C
= 96,484 C mol-1 (usually rounded up to 96,500 C mol-1 in high school
chemistry)

Faraday's Laws of Electrolysis Calculations:

Q = n(e-) F

Q = quantity of electricity measured in coulombs (C)

n(e-) = moles of electrons used
F = the Faraday (Faraday constant) = 96,500 C mol-1

We can calculate the mass of a substance produced during an electrolysis experiment by:

i) calculating the moles of electrons used: n(e-) = Q/F

ii) using the moles of electrons to calculate the moles of substance produced using
the balanced reduction (or oxidation) half reaction equation

iii) using the moles of substance to calculate the mass of substance:

mass = moles molar mass

Worked Examples: Q = n(e-)F calculations

Question 1. Calculate the quantity of electricity obtained from 2 moles of electrons

Solution:

(Based on the StoPGoPS approach to problem solving.)

1. What is the question asking you to do?

Calculate the quantity of electricity

Q=?C
 2. What data (information) have you been given in the question?

Extract the data from the question:

moles of electrons = n(e-) = 2 mol
Faraday constant = F = 96,500 C mol-1 (data sheet)

3. What is the relationship between what you know and what you need to find out?

Write the equation:

Q = n(e-) F

4. Substitute the values into the equation and solve for Q:

Q = 2 96,500 = 193,000 C

5. Is your answer plausible?

Use your calculated value of Q and the Faraday constant F to calculate moles of electrons
and compare that to the value given in the question.
Q = n(e-)F
193,000 = n(e-) 96,500
n(e) = 193,000 96,500 = 2
Since we were told there were 2 moles of electrons in the question, we are reasonably
confident that our value for Q is correct.

6. State your solution to the problem:

Q = 193,000 C

Question 2. Calculate the moles of electrons obtained from 250 C of electricity.

Solution:

(Based on the StoPGoPS approach to problem solving.)

1. What is the question asking you to do?

Calculate the moles of electrons

n(e-) = ? mol

2. What data (information) have you been given in the question?

Extract the data from the question:

Q = 250 C
F = 96,500 C mol-1 (data sheet)

3. What is the relationship between what you know and what you need to find out?
 Write the equation:
Q = n(e-) F
Rearrange the equation to find moles of electrons, n(e-):
n(e-) = Q F

4. Substitute the values into the equation and solve for n(e-):

n(e-) = 250 96,500 = 2.59 10-3 mol

5. Is your answer plausible?

Use your calculated value of n(e-) and the Faraday constant F to calculate quantity of
charge (Q) required and compare that to the value given in the question.
Q = n(e-) F
Q = 2.59 10-3 96,500 = 250 C
Since this value of Q agrees with that given in the question we are reasonably confident
that our value for n(e-) is correct.

6. State your solution to the problem:

n(e-) = 2.59 10-3 mol

Worked Examples: Calculating amount of substance

deposited
Question 1: Calculate the moles of copper metal that can be produced by the electrolysis of
molten copper sulfate using 500 C of electricity.

Solution:

(Based on the StoPGoPS approach to problem solving.)

1. What is the question asking you to do?

Calculate the moles of copper metal

n(Cu(s)) = ? mol

2. What data (information) have you been given in the question?

Extract the data from the question:

electrolyte: CuSO4(l)
Q = 500 C
F = 96,500 C mol-1 (data sheet)

3. What is the relationship between what you know and what you need to find out?
 Write the reduction reaction equation for the production of copper metal from molten
copper sulfate:
Cu2+ + 2e- Cu(s)

Calculate the moles of electrons, n(e-):

n(e-) = Q F
= 500 96,500
= 5.18 10-3 mol

4. Determine the moles of Cu(s) produced using the balanced reduction reaction equation
(mole ratio):

1 mole of electrons produces mole of Cu(s)

Therefore 5.18 10-3 moles of electrons produces 5.18 10-3
n(Cu(s)) = 2.59 10-3 mol

5. Is your answer plausible?

Use your calculated value of n(Cu(s)) and the Faraday constant F to calculate quantity of
charge (Q) required and compare that to the value given in the question.
Q = n(e-)F
n(e-) = 2 n(Cu) = 2 2.59 10-3 = 5.18 10-3 mol
F = 96,500
Q = 5.18 10-3 96,500 = 500 C
Since this value for Q is the same as that given in the question, we are reasonably
confident that our calculated value for moles of copper deposited is correct.

6. State your solution to the problem:

n(Cu(s)) = 2.59 10-3 mol

Question 2. Calculate the mass of silver that can be produced by the electrolysis of 1 mol L-1
AgCN(aq) using 800 C of electricity

Solution:

(Based on the StoPGoPS approach to problem solving.)

1. What is the question asking you to do?

Calculate the mass of silver deposited

m(Ag(s)) = ? g

2. What data (information) have you been given in the question?

 Extract the data from the question:
electrolyte: AgCN(aq)
[AgCN(aq)] = 1 mol L-1 (standard solution)
Q = 800 C
F = 96,500 C mol-1 (data sheet)

3. What is the relationship between what you know and what you need to find out?

Write the reduction reaction equation for the production of silver metal from the aqueous
solution:
Ag+(aq) + e- Ag(s)

Calculate the moles of electrons, n(e-):

n(e-) = Q F
n(e-) = 800 96,500 = 8.29 10-3 mol

Determine the moles of Ag(s) produced using the balanced reduction reaction equation
(mole ratio):
1 mole of electrons produces 1 mole of Ag(s)
Therefore 8.29 10-3 moles of electrons produces 8.29 10-3 moles Ag(s)

4. Calculate the mass of Ag(s)

moles (Ag) = mass (Ag) molar mass (Ag)
So, mass (Ag) = moles (Ag) molar mass (Ag)

moles (Ag) = 8.29 10-3 mol

molar mass (Ag) = 107.9 g mol-1 (from periodic table)

mass (Ag) = 8.29 10-3 mol 107.9 g mol-1

= 0.894 g

5. Is your answer plausible?

Use your calculated value of m(Ag(s)) and the Faraday constant F to calculate quantity of
charge (Q) required and compare that to the value given in the question.
n(e-) = n(Ag) = mass molar mass = 0.894 107.9 = 8.29 10-3 mol
Q = n(e-)F = 8.29 10-3 mol 96,500 = 800 C
Since this value of Q agrees with that given in the question, we are reasonably confident
that our calculated mass of silver is correct.

6. State your solution to the problem:

m(Ag(s)) = 0.894 g

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Worked Examples: Q = n(e-)F and Q = It

Question 1. What mass of copper could be deposited from a copper(II) sulphate solution using a
current of 0.50 A over 10 seconds?

Solution:

(Based on the StoPGoPS approach to problem solving.)

1. What is the question asking you to do?

Calculate the mass of copper deposited

m(Cu(s)) = ? g

2. What data (information) have you been given in the question?

Extract the data from the question:

electrolyte: copper(II) sulphate solution, CuSO4
current: I = 0.50 A
time: t = 10 seconds
F = 96,500 C mol-1 (data sheet)

3. What is the relationship between what you know and what you need to find out?

Calculate the quantity of electricity:

Q=Ixt
I = 0.50 A
t = 10 seconds
Q = 0.50 10 = 5.0 C

Calculate the moles of electrons:

n(e-) = Q F
Q = 5.0 C
F = 96,500 C mol-1
n(e-) = 5.0 96,500
= 5.18 10-5 mol

Calculate moles of copper using the balanced reduction half reaction equation:
Cu2+ + 2e- Cu(s)
1 mole of copper is deposited from 2 moles electrons (mole ratio)
moles(Cu) = n(e-)
 = 5.18 10-5
= 2.59 10-5 mol

4. Calculate mass of copper:

mass = moles molar mass

moles (Cu) = 2.59 10-5 mol
molar mass (Cu) = 63.55 g mol-1 (from Periodic Table)
mass (Cu) = (2.59 10-5) 63.55
= 1.65 10-3 g
= 1.65 mg

5. Is your answer plausible?

Use your calculated value of m(Cu(s)) and the Faraday constant F to calculate quantity of
charge (Q(b)) required and compare that to the value of Q(a) = It given in the question.
Q(a) = It = 0.50 10 = 5 C

Q(b) = n(e-)F
n(e-) = 2 n(Cu) = 2 [m(Cu) Mr(Cu)] = 2 [(1.65 10-3) 63.55] = 2 2.6 10-5
= 5.2 10-5 mol
Q = 5.2 10-5 96,500 = 5

Since Q(a) = Q(b) = 5 C, we are reasonably confident that our calculated mass of copper is
correct.

6. State your solution to the problem:

m(Cu(s)) = 1.65 10-3 g (or 1.65 mg)

Question 2. Calculate the time required to deposit 56 g of silver from a silver nitrate solution
using a current of 4.5 A.

Solution:

(Based on the StoPGoPS approach to problem solving.)

1. What is the question asking you to do?

Calculate time required

t = ? seconds

2. What data (information) have you been given in the question?

Extract the data from the question:

mass silver = m(Ag(s)) = 56 g
 current = I = 4.5 A
F = 96,500 C mol-1 (from data sheet)

3. What is the relationship between what you know and what you need to find out?

Calculate the moles of silver deposited:

moles (Ag) = mass (Ag) molar mass (Ag)
mass Ag deposited = 56 g
molar mass = 107.9 g mol-1 (from Periodic Table)
moles (Ag) = 56 107.9
= 0.519 mol

Calculate the moles of electrons required for the reaction:

Write the reduction reaction equation:
Ag+ + e- Ag(s)
From the equation 1 mole of Ag is deposited by 1 mole of electrons (mole ratio)
therefore 0.519 moles of Ag(s) is deposited by 0.519 moles of electrons
n(e-) = 0.519 mol

Calculate the quantity of electricity required:

Q = n(e-) F
n(e-) = 0.519 mol
F = 96,500 C mol-1
Q = 0.519 96,500 = 50,083.5 C

4. Calculate the time required:

Q=It
Rearrange the equation to find t:
t=QI
Q = 50,083.5 C
I = 4.5 A
t = 50,083.5 4.5
= 11,129.67 seconds
t = 11,129.67 60 = 185.5 minutes
t = 185.5 60 = 3.1 hours

5. Is your answer plausible?

Use your calculated value of time in seconds, the Faraday constant F and the current
given in the question to calculate the mass of Ag you could deposit and compare that to
the value given in the question.
Q = It = 4.5 11,129.67 = 50083.5 C
Q = n(e-)F
so, n(e-) = Q F = 50083.5 96,500 = 0.519 mol
n(Ag) = n(e-) = 0.519 mol
m(Ag) = n(Ag) Mr(Ag) = 0.519 107.9 = 56 g
 Since this value for the mass of silver is the same as that given in the question, we are
reasonably confident that the time in seconds we have calculated is correct.

6. State your solution to the problem:

t = 11,129.67 seconds (or 185.5 minutes or 3.1 hours)