Some basic concepts in electrochemistry and entropy

Entropy is a measure of the dispersal of energy at a specific temperature. Entropy can also be
thought of as a measure of the randomness or disorder of a system.

Under standard conditions and for a mole of substance, the unit of standard molar entropy, S —O ,
is J K–1 mol–1. Standard molar entropy is the entropy of one mole of substance in its standard
state. The symbol —O indicates that the entropy is at standard conditions.

Findings:

In general, gases generally have much higher entropy values than liquids, and liquids have higher entropy
values than solids. There are exceptions.
Simpler substances with fewer atoms have lower entropy values than more complex substances with a
greater number of atoms. For example, for calcium oxide, CaO, S —O = 39.7 J K–1 mol–1 but for calcium
carbonate, CaCO3, S —O = 92.9 J K–1 mol–1. Carbon monoxide, CO, has a lower entropy value than carbon
dioxide, CO2.

Calcula8ons rela8ng to entropy:

Note that:

We need to take account of the stoichiometry of the equation (as we did in calculations
involving ΔH —O ).

When looking up entropy values in tables of data, we need to choose the data for the correct
state, solid, liquid or gas.

The units can be tricky

What can this imply?

A spontaneous reac8on would increase total entropy.

Gibbs free energy:

- We ignored surroundings in this equa8on

- A nega8ve change in Gibbs Free Energy means a reac8on is spontaneous

- Calcula8ng Gibbs Free Energy change of a reac8on:
Electrochemistry

RED CAT
AN OX

Example: CuCl2 solu8on

Anode:

Cathode:
What ions would be discharged preferen8ally?

Standard hydrogen electrode

Posi8ve voltage: Easier to be reduced compared to H+
Nega8ve voltage: Harder to be reduced than H+
Inorganic chemistry: transi8on metal complexes

Common geometry:

4-coordinate:

5-coordinate:

6-coordinate:

Isomers, high spin low spin