Redox II part 1

The point of this topic is to generate electricity utilising simple redox reactions.

Below is a simple diagram of an electrochemical cell where the redox reactions take place. A cell consists
of two electrodes, two solutions, a voltmeter and a salt bridge.

A salt bridge is usually something like KCl or KNO 3. It completes the circuit and also balances the charge by
allowing ions to flow between the two solutions.

The two solutions are aqueous solutions of ions from ionic compounds, in this example, Zn 2+ and Cu2+.
There is also SO42- in both solutions but it doesnt take part in the reaction.

The electrodes
The electrodes are either made from the species involved in the reaction, in this case, Cu and Zn or
platinum.

If you have for example one ion in solution then the metal of that ion can be used e.g. Zn 2+ ions in solution
and a Zn electrode.

If you have two ions in the same solution e.g. Fe2+ and Fe3+ then you will need a platinum electrode.
Platinum is also used as it is unreactive and a good conductor of electricity.

If a gas is involved you also need to use platinum.

How it works
All that occurs is a simple redox reaction. Oxidation occurs at one electrode and reduction at the other.

there are no complicated reactions in this topic, they are all just redox.
The more reactive metal is oxidized (in this case Zn Zn2+) and the electrons that it loses are released
into the circuit. These electrons flow to the other electrode where reduction occurs (Cu 2+ Cu).

Anode versus cathode

This causes a lot of confusion. Students often refer back to electrolysis at GCSE where they are told that
the cathode is negative and the anode is positive. This is correct for electrolysis.

In electrolysis electricity is supplied via a power supply. In this topic we are generating electricity. Two
very different situations!

So just remember for redox II:

ANODE: A = anode N = negative O = oxidation

Potentials
In simple terms, the voltmeter measures a voltage difference between the two electrodes. Or in more
physics sounding language, the cell potential, often referred to as the EMF or Ecell.

Anytime that charge (electrons) flows, there is a potential (voltage) that can be measured.

this is chemistry and not physics so you dont need to worry about this too much. Just think of it as
measuring a voltage. If you see the word potential, its just a voltage. Keep it simple!

In order to be able to calculate this difference in voltage, each oxidation and reduction reaction has its
own potential associated with it.

Or you can think of it as each electrode having its own potential, known as the electrode potential,
shown by a Eo symbol.

the important part of this topic is to understand what the electrode potential values tell you. In short,
it tells you how easily a species can be oxidised or reduced. We will look at this in more detail.

just to satisfy anybody doing physics . The voltmeter is a high resistance voltmeter and no current
passes through it. This is just there to measure the cell potentials. When the actual redox reactions
take place it wont be there.

Standard Hydrogen Electrode

Examiners often ask about the standard hydrogen electrode. The purpose of this electrode is to enable
you to measure the potential of another species at the other electrode Eo values.

Remember in science everything has to be measured against a standard value to give it meaning and to
allow things to be compared.
 Hydrogen gas at 1 atm pressure

Measured at 298K
Platinised platinum electrode

Solution containing hydrogen ions

at 1.0 moldm-3

Think of this as just another electrode. As was mentioned above, when a gas is used, the electrode is
platinum.

The standard hydrogen electrode is set to 0 volts. Its not really 0 volts but as it is a standard, someone
decided that it is 0. Therefore, any voltage registered in the voltmeter measured must have come from
the other electrode. This is the way all the Eo values in the electrochemical series are worked out.

Standard conditions: solutions have a concentration of 1.00 mol dm-3 (H+ ions of 1.00 mol dm-3), a
temperature of 298 K and a pressure of 101 kPa (or 1 atm).

the hydrogen electrode is difficult to use. There are other standard electrodes such as the calomel
electrode. However exam questions are almost all on the hydrogen electrode.

it is worth being able to draw the above apparatus for the standard hydrogen electrode and also for a
normal cell as shown at the start of this tutorial.

The Electrochemical Series

The result of working out all the electrode potentials is a table like the one shown below. This is only part
of the electrochemical series as there are a huge number of different species.

in the electrochemical series, all the half equations are written as reductions. But as we are doing
redox reactions we need one oxidation and one reduction. Therefore you always have to turn one fo
the equations round. We will look at this below.
What do the Eo values tell you?
They tell you: what is the best reducing and oxidising agents (and worst) and what reactions are likely to
occur.
an electron acceptor
An oxidising agent gets reduced, therefore it is:

an electron donor
A reducing agent gets oxidised, therefore it is:

In the table above, or any other table of these values:

reducing agents are always on the right hand side and oxidising agents are always on the left hand side

students often get confused by this. Think about it. A reducing agent gets oxidised. Therefore that
species must increase in oxidation state. The half-equations show exactly what is happening:

e.g. Zn2+ + 2e- Zn

The reducing agent must be Zn as it is can only become Zn 2+. If someone said Zn 2+ is the oxidising
agent then this would imply that Zn 2+ is increasing to an oxidation state higher than 2+. Firstly this is
impossible but also the equation only has Zn and Zn2+ in it! Use the equations.

Following on from this:

the more negative the potential the better a reducing agent it is

In the table above, the most negative value is for the reduction of Zn2+:

Zn2+(aq) + e- Zn(aq)
Therefore, Zn is the best reducing agent.

This means, in the table above, Zn will reduce everything with a more positive potential. i.e. it will
reduce the species on the left hand side that have more positive potentials. For example, Fe 3+ Fe2+, Ag+
Ag etc.

And we can also say that:

the more positive the potential then the better an oxidising agent it is

This means that MnO4- is the best oxidising agent in the table. And will therefore oxidize anything (on the
right hand side) with a lower Eo value. For example, Zn Zn2+, Fe2+ Fe3+ etc.

Ecell Values
Now that you know what the Eo values mean, you need to use them to calculate the Ecell values, which are
just simple subtractions.

Ecell = Eo of the more positive value Eo of the more negative value

The Ecell value tells us if a reaction is likely to occur or not. If E cell is a positive value then the reaction is
likely occur. The higher the value, the more likely the reaction is to happen.

you do not have to multiply the Eo value by anything ever.

You can think of this topic as bit like entropy i.e. they both predict whether a reaction is likely to occur or
not.

Ecell is proportional to both lnK and S

If the Ecell value increases, then the equilibrium lies further to the right.