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BASIC ELECTROLYSIS CALCULATIONS - Week 11

The Faraday constant

 

Coulombs

The coulomb is a measure of the quantity of electricity. If a current of 1 amp flows for 1 second, then 1 coulomb of electricity has passed.

That means that you can work out how much electricity has passed in a given time by multiplying the current in amps by the time in seconds.

 

Number of coulombs = current in amps x time in seconds

If you are given a time in minutes or hours or days, then you must convert that into seconds before you do anything else.

For example, if a current of 2 amps flows for an hour, then:

Number of coulombs = 2 x 60 x 60 = 7200

(60 minutes in each hour; 60 seconds in each minute.)

The Faraday

Electricity is a flow of electrons. For calculation purposes, we need to know how to relate the number of moles of electrons which flow to the measured quantity of electricity.

The charge that each electron carries is 1.60 x 10 -19 coulombs. If you ever needed to use it in an exam, you would be given the value.

1 mole of electrons contains the Avogadro constant, L, electrons - that is 6.02 x 10 23 electrons. You would also be given that in an exam if you needed to use it.

That means the 1 mole of electrons must carry

6.02 x 10 23 x 1.60 x 10 -19 coulombs

= 96320 coulombs

This value is known as the Faraday constant.

.

That is 96500 coulombs per mole. So 96500 coulombs is called 1 faraday.

Using the Faraday constant in calculations

Example 1

 

Calculate the mass of silver deposited at the cathode during the electrolysis of silver nitrate solution if you use a current of 0.10 amps for 10 minutes.

F = 9.65 x 10 4 C mol -1 (or 96500 C mol -1 if you prefer). A r of Ag = 108.

1.The first thing to do is to work out how many coulombs of electricity flowed during the electrolysis.

Number of coulombs = current in amps x time in secondscoulombs of electricity flowed during the electrolysis . Number of coulombs = 0.10 x 10 x

Number of coulombs = 0.10 x 10 x 60 = 60. Number of coulombs = current in amps x time in seconds Now look at the

Now look at the equation for the reaction at the cathode:

 
 

:

1

:

1

1 mol of electrons gives 1 mol of silver, Ag.

1 mol of electrons gives 1 mol of silver, Ag.

Now put the numbers in. 1 mol of electrons is 1 faraday.

96500 coulombs give 108 g of silver.

96500 coulombs give 108 g of silver.

So, if 96500 coulombs give 108 g of silver, all you have to do is to work out what mass of silver would be produced by 60 coulombs.

Mass of silver = 60/96500 x 108 g = 0.067 g

Mass of silver = 60/96500 x 108 g = 0.067 g

Example 2

 

This example shows you how to do the calculation if the product you are interested in is a gas.

Calculate the volume of hydrogen produced (measured at room temperature and pressure - rtp) during the electrolysis of dilute sulphuric acid if you use a current of 1.0 amp for 15 minutes.

F = 9.65 x 10 4 C mol -1 (or 96500 C mol -1 ). The molar volume of a gas at rtp = 24 dm 3 mol -1 .

Start by working out how many coulombs of electricity flowed during the electrolysis.

Number of coulombs = current in amps x time in seconds

Number of coulombs = current in amps x time in seconds

Number of coulombs = 1.0 x 15 x 60 = 900 Now look at the
Number of coulombs = 1.0 x 15 x 60 = 900
Now look at the equation for the reaction at the cathode:
2
:
1
Write down the essential bits in words:
2
mol of electrons give 1 mol of hydrogen, H 2 .
Now put the numbers in. Two moles of electrons is 2 faradays.
2
x 96500 coulombs give 24 dm 3 H 2 at rtp.
So, if 2 x 96500 coulombs give 24 dm 3 H 2 , work out what volume of hydrogen would be
produced by 900 coulombs.
Volume of hydrogen = 900/(2 x 96500) x 24 dm 3 = 0.11 dm 3
Example 3
This example shows you what to do if the question is reversed.
How long would it take to deposit 0.635 g of copper at the cathode during the electrolysis of
copper(II) sulphate solution if you use a current of 0.200 amp.
F = 9.65 x 10 4 C mol -1 (or 96500 C mol -1 ). A r of Cu = 63.5.
This time you can't start by working out the number of coulombs, because you don't know
the time. As with any other calculation, just start from what you know most about. In this
case, that's the copper, so start with the electrode equation.
2
:
1
Write down the important bits of this in words:
2
mol of electrons give 1 mol of copper, Cu.
Now put the numbers in. 1 mol of electrons is 1 faraday.
2
x 96500 coulombs give 63.5 g of copper.
You need to work out how many coulombs give 0.635 g of copper.
Number of coulombs = 0.635/ 63.5 x 2 x 96500 = 1930

Now what?

You know how many coulombs you need, and you know what the current was in amps. You have got all the information you need to work out the time.

Number of coulombs = current in amps x time in secondshave got all the information you need to work out the time. 1930 = 0.200 x

1930 = 0.200 x ttime. Number of coulombs = current in amps x time in seconds t = 1930/0.200 =

t = 1930/0.200 = 9650 seconds.= current in amps x time in seconds 1930 = 0.200 x t Don't waste time

Don't waste time trying to convert that into minutes or hours (unless the exam question specifically asks you to).

Example 4

Another gas example:

Calculate the volume of oxygen produced (measured at room temperature and pressure - rtp) during the electrolysis of sodium sulphate solution if you use a current of 0.50 amp for 30 minutes.

F = 9.65 x 10 4 C mol -1 (or 96500 C mol -1 ). The molar volume of a gas at rtp = 24 dm 3 mol -1 .

Start by working out how many coulombs of electricity flowed during the electrolysis.

Number of coulombs = current in amps x time in secondsmany coulombs of electricity flowed during the electrolysis. Number of coulombs = 0.50 x 30 x

Number of coulombs = 0.50 x 30 x 60 = 900Number of coulombs = current in amps x time in seconds Now we need to look

Now we need to look at the equation for the reaction at the anode. Unfortunately, there are two ways of looking at this, and you may come across either of them.

The first one releases oxygen from water molecules:

of them. The first one releases oxygen from water molecules: The alternative way releases oxygen from

The alternative way releases oxygen from hydroxide ions from the ionisation of the water:

oxygen from hydroxide ions from the ionisation of the water: Write down the essential bits in

Write down the essential bits in words. Both ways of looking at it say the same thing:

Releasing 1 mol of oxygen, O 2 , involves 4 mol of electrons. 2 , involves 4 mol of electrons.

Now put the numbers in. Four moles of electrons is 4 faradays.

4 x 96500 coulombs give 24 dm 3 O 2 at rtp. So, if 4
4 x 96500 coulombs give 24 dm 3 O 2 at rtp.
So, if 4 x 96500 coulombs give 24 dm 3 H 2 , work out what volume of oxygen would be
produced by 900 coulombs.
Volume of oxygen = 900/(4 x 96500) x 24 dm 3 = 0.056 dm 3
Practice questions

1. Nickel(II) sulphate solution was electrolysed using a carbon anode and an iron key as the cathode. A nickel coating was formed on the key, and oxygen was given off at the anode.

a) Write the cathode equation.

b) What mass of nickel would be deposited on the iron key if a current of 0.30 amps

flowed for 15 minutes? (F = 96500 C mol-1; Ar Ni = 58.7)

c) Write the anode equation.

d) What volume of oxygen measured at room temperature and pressure would be

produced in the same time? (Molar volume of a gas at rtp =24 dm3 mol-1)

2. a) Suppose you electrolysed dilute sulphuric acid using inert electrodes in a piece of apparatus that enabled you to collect the gases produced over water into measuring cylinders.

(a) How long would it take you to fill a 100 cm3 measuring cylinder with hydrogen if you used a current of 2.0 amps ,everything being done at room temperature? (F = 96500 C mol-1; molar volume of a gas at rtp =24 dm3 mol-1)

b) What current would you have to use in order to fill the measuring cylinder in exactly 5

minutes?