ELECTROCHEMISTRY- PART1

What is electrolysis?

In simple terms if we had a substance for example water, H2O and we want a

chemical change to occur that would separate water into hydrogen gas and oxygen

gas. Normally, water on its own will not facilitate this reaction to occur so we can

use electrolysis to force this reaction to occur.

It does this by using electricity to make a chemical change occur that would not

happen spontaneously. Electrolysis is often used on compounds that would break it

down into the elements that make it up. We will look at two (2) common examples

that will explain what electrolysis is about.

Before we do this, we need to understand concepts such as oxidation and

reduction.
Oxidation and Reduction

Rules

Let’s

discuss these rules briefly:

1. Elements by itself: These are called free elements and can exist naturally on

its own e.g. oxygen (O2), Carbon (C), sodium (Na), Chlorine (Cl2), Sulphur

(S6) and Phosphorus (P4). Therefore, its oxidation number is zero ‘0’.

2. Monatomic ions: Essentially, its an element that can only exist as one atom.

E.g. Magnesium (Mg2+).

The rest of the rules we will be explained in relation to this table.

1.

Note: this is a neutral compound since it doesn’t have a charge after all of the
elements. Hence, the sum of the individual charges must sum to zero.

2.

3.
Note: there aren’t any rules listed above for carbon but what we do know is the
sum of any neutral compound should be zero.

4.

5.

The reason why we need to know about oxidation numbers is because in

electrolysis electrons are constantly being added and removed thus altering the

charge and this helps us identify what products would be discharged at the anode

and at the cathode.

Now, when something loses electrons, its charge increases, and it is said to be

oxidized. However, when something gains electrons, its charge decreases, and it

is said to be reduced.
EXAMPLE 1: Electrolysis of sodium chloride (NaCl)

We want to use electrolysis to split salt into sodium and chlorine.

Now, you may wonder why it is Cl2 and not Cl. It’s because chlorine belongs to a

group of diatomic elements and it always forms groups of two not just a single

atom. Therefore, you never find one of these atoms alone or by itself.
This is regular table salt and if this was left out for a long time this reaction still

will not occur and therefore, we must resort to electrolysis to force this reaction to

occur.

This is a micro view of how this process is setup.

Note that the table salt is not the powdered form but
has to be in molten state meaning liquid which occurs at extremely high

temperatures.

Let’s expand the view to really understand what’s taking place with the electrons.
Now, we need to understand some minor concepts before we dive deeper into

electrolysis.

This is why electrolysis uses a conductive material because we need to conduct

electricity in order for it to force electrons in and out of a solution.

This is important to note because a question may come where you need to explain

how does a metal conduct electricity as opposed to an electrolyte.

You also need to understand how to distinguish from weak and strong electrolytes

and that whenever you associate with a weak electrolytes it means that it is able to

partially ionize and its essentially a poor conductor of electricity.

As you can see the ions in the cell are all over since its in the liquid state and its

placed between two electrodes of some material that has the ability to pull and

push electrons in and out of the solution.

Now, remember from the stoichiometric equation, sodium was reduced and

therefore, that will take place at the cathode and we also know that chlorine was

oxidized and that will take place at the anode. Another way to look at it is to look

at the charge. Remember from physics, unlike charges attract and like charges

repel. Therefore, the cathode is negative, so it looks for a positively charged ion in

this case the sodium and the anode is positive, and it looks for a negatively charged

ion in this case the chlorine.

In the picture above it show the charges are removed in the chlorine and sodium

ions.

How did this take place?

Firstly, the anode, pulls electrons from the chlorine ion and then those electrons are

transferred to the cathode which pushes the electrons from the chlorine to the

sodium. Since the chlorine lost electrons the negative one charge increase by 1 and

went to zero. Since the sodium gained electrons the positive charge decreased by 1

and went to zero.

Now, remember chlorine exists as a diatomic gas so after 2 electrons are removed

from 2 chlorine atoms it will clump together to form Cl2. This is a gas so it will

float away to the top and the process will continue.

Now I want to write half reactions for the electron transfer that is taking place.
Theoretically, for the oxidation side it is correct but in chemical equations we don’t

minus electrons, so it has to be rewritten in the form shown below.

In any half reaction, if the number of electrons are placed to the right side it means

it is oxidation in this case its loosing 2 electrons to form chlorine gas.

The final step is to balance and combine these half reactions.

So essentially, we need to understand what are the ions that are being produced, we

need to get back the same reaction we had initially after we combined, and we

need to balance the number of electrons. If the we had balanced the chemical

reaction initially, we would not need to multiply by 2.

EXAMPLE 2: Electrolysis of water (H2O)

Now, if water were to be split using electrolysis it would for hydrogen and oxygen

but remember to check the diatomic elements list and you would see they belong to

that group. Since this is the

case, we cannot just put H

and O but H2 and O2.

Just like the sodium chloride example this process does not happen on its own

hence it’s not spontaneous. You can have water in a glass for a long time and it

still will not separate into hydrogen and oxygen on its own.

Now this is the setup of the process. You may have observed a difference than the

previous example. In this case it has upside down test tubes and the reason for this

is because you want to control the containment of the gases being produced. Also

remember form ionic compounds that they are able to conduct electricity. In this
process we must add some Sulphuric acid which is an electrolyte because

electricity cannot be conducted in pure or distilled water.

So now we want to decide what products will be discharged at the anode and

cathode sites. Take a look at the redox equation, the oxygen is being oxidized to

form O2 so that oxidation process will take place at the anode since at the anode

oxidation occurs and since hydrogen is reduced that will occur at the cathode.

Now, something to notice is that when these gases are to be produced, the level of

water in the test tubes drops and the reason for that is because the gases exert a

pressure or a force on the water. The test tube on the right has a lower level since

twice the amount of hydrogen gas is produced.

Remember the balanced stoichiometric equation starts off with 2 molecules of

water that is why we have 2 molecules initially. Now we need to combine these

half reactions.
Notice, after simplifying the above equations we got back the initial balanced

equation.