5072 Chemistry Syllabus Notes

Electrolysis

Electrolysis is the conduction of electricity by an ionic compound (an electrolyte), when

molten or dissolved in water, leading to the decomposition of the electrolyte.

Implications of electrolysis:

Electrolysis is the evidence for the existence of ions which are held in a lattice when
solid but which are free to move when molten or in solution.

Case Study: Electrolysis of sodium chloride

Molten sodium chloride can be electrolyzed to form molten sodium metal and chlorine
gas. Molten sodium chloride has mobile sodium and chloride ions that are able to
conduct a current. As they conduct the electrical current, the ions are transformed by
the free electrons in the electric current to form the electrolysis products.

When electrolyzed using inert electrodes, molten sodium chloride decomposes under
the following reactions:

Cathode reaction:
Na+ (l) + e- ⟶ Na (l)

Anode reaction:

2 Cl- (l) ⟶ Cl2 (g) + 2 e-

Predicting electrolysis products:

The electrolysis of molten binary ionic compounds will form the constituent elements of
the compound. Examples include molten sodium chloride (refer to above case study) as
well as molten magnesium oxide.

In the electrolysis of aqueous ionic compounds or of non-binary ionic compounds,

selective discharge of ions occur according to the electrochemical discharge series.
The order of selective discharge of cations is contingent on the reactivity series of
metals. As we move up the reactivity series to the more reactive metals, the ease of
discharge is decreased. Thus less reactive metals are selectively discharged before
more reactive metals.

The order of discharge of anions is slightly more tricky. As a general rule, the more
stable the anion is, the more difficult it is to discharge the ion. As such, these ions will
be lower in the discharge series. Nitrate ions for example, are very stable due to the
shape of the ion as well as the electronegativity of both nitrogen and oxygen.

An implication of selective discharge is that when some aqueous ionic compounds are
electrolyzed, the ionic compound itself does not decompose but rather, water is
electrolyzed in its stead. For example, in the electrolysis of dilute sodium chloride
solution, sodium chloride itself is not broken down but the water in the solution does;
forming hydrogen and oxygen gas.

A factor affecting the products of electrolysis of aqueous ionic compounds is the

concentration effect. As an ion becomes more concentrated in a solution, it will collide
with the electrode more often, increasing the number of such ions being discharged.

A prominent example of this is with concentrated sodium chloride. As the chloride ions
are present in large amounts within the solution, they are able to compete with the
hydroxide ions for discharge priority. As such, the anode product of such electrolysis is
chlorine gas instead of the typical oxygen gas.

However, this effect is limited by the electrical affinity of the ions present in the solution.
For example, chloride ions are able to compete with hydroxide ions when present in a
concentrated solution as the ions are not so far apart in terms of their ability to lose
electrons (due to the large size of chloride ions). However, sodium metal is not formed
from the electrolysis of concentrated sodium chloride as sodium’s ability to accept
electrons is vastly lesser than hydrogen’s. Thus, the difference in electrochemical
discharge potential between these two elements is sufficiently great so as to prevent the
discharge of sodium.

Do note that all of the above examples are predicated on the assumption that inert
electrodes are used.

Use of non-inert electrodes

When non-inert anodes are used, the anode decomposes in the electrolysis to form
metal ions. This is because the free electrons present within the structure of these
metals are drawn by the cell out of the anode. Thus, the positive lattice within the metal
disintegrates to form mobile positive metallic ions.

Case study: Purification of copper

Copper metal can be purified using the electrolysis of aqueous copper(II) sulfate. In this
process, the impure copper metal is attached as the anode.

The copper within the anode decomposes to form copper ions:

Cu (s) ⟶ Cu2+ (aq) + 2 e-

The impurities on the impure copper metal will thus be left at the bottom of the
electrolysis tank as the impurities do not participate in the electrolysis reaction.

At the cathode, copper ions are discharged from the solution to form copper metal on
the cathode.

Cu2+ (aq) + 2 e- ⟶ Cu (s)

Thus, pure copper is re-deposited onto the cathode.

Case Study: Copper electroplating

The desired object is attached as the cathode while the electroplating metal (copper) is
attached as the anode. A suitable electrolyte that contains the cation of the
electroplating metal is used (aqueous copper(II) sulfate).

During electrolysis, the non-inert copper anode will decompose to form copper ions
which are discharged into the solution.

Cu (s) ⟶ Cu2+ (aq) + 2 e-

Copper from the solution will also be discharged onto the cathode (desired object), thus
electroplating the object.

Cu2+ (aq) + 2 e- ⟶ Cu (s)

One use of electroplating is the production of electrical contacts. Gold, although being a
very desirable material for manufacturing electrical contacts due to its relative inertness
and excellent electrical conductivity, is both too expensive and too soft to manufacture
entire contacts. Thus, gold is electroplated onto electrical contacts to form a connective
layer without experiencing any of the abovementioned side-effects.

Electrical cells

When two metals of differing reactivity are connected while immersed in a conducting
solution, the two metals exert an electrical potential onto each other. More reactive
metals are more electropositive than less reactive metals. Thus, more reactive metals
will “donate” delocalized electrons to less reactive metals, effectively creating a current
flow.
The electrical potential difference of a cell (linked to e.m.f) is determined by the
difference in reactivity of the two metal electrodes. For example, sodium and
magnesium will not have as much potential difference than sodium and copper.

In electrical cells, the more reactive metal is always the anode while the less reactive
metal is the cathode.

General rule of electrolysis/electric cell/hydrogen fuel cell

Cathode reactions always reduce while anode reactions always oxidize.