Preferential discharge of ions

The ions present during electrolysis are derived from the reacting substances.
The negative ions (anions) drift toward the anode and positive ions (cations) drift to the

cathode.
The main factor that influences the preferential discharge of ions is the position of the ion in the
electrochemical series.

Ions at the top of the series are most

stable and hardest to discharge while ions

at the bottom of the series are least stable

and easiest to discharge. The lower the

ion in the electrochemical series, the

more likely it is to be discharged.

The electrochemical series for anions and cations

In the electrolysis of dilute sodium chloride solution using inert electrodes the ions

present are: Na+, Cl-, H+ and OH-

The Cl- and OH- ions move towards the anode. OH- ions are preferentially discharged

because they are in dilute solution (more OH- than Cl-) and are lower in the
electrochemical series of anions. The reaction produces effervescence as oxygen gas is
evolved: 4OH-  2H2O + O2 +4e-

Na+ and H+ ions move to the cathode and H+ is discharged because it is lower in the
electrochemical series of cations. Effervescence occurs as hydrogen gas is evolved:

2H+ +2e-  H2
In a concentrated sodium chloride solution, Cl- ions will discharge at the anode

because of their higher concentration and chlorine gas would be evolved. At the
cathode however the H+ will discharge because they are lower in the series.
Quantitative electrolysis

Volumes of gases and masses of substances produced during electrolysis can be

calculated using mole concept. Michael Faraday first proposed that the mass of

substance produced at an electrode during electrolysis is directly proportional to the

quantity of electricity passing through the electrolytic cell.

The quantity of electricity/ quantity of electrical charge is symbolised Q and is measured

in coulumbs C.
The flow of a single electron from the anode to cathode during electrolysis has an
extremely small electrical charge. The flow of 1C of electricity through a circuit is equal
the passage of 6.25 x 1028 electrons.

The quantity of electricity flowing through an electrolytic cell during electrolysis

depends on two factors

 The rate of flow of electrical charge (the current, I measured in amperes/ amps A)

1 amp = 1C or 6.25 x 1028 electrons flowing for 1s

 The length of time, t that the current flows for; measured in seconds, s.

The quantity of electricity or electrical charge can be calculated using the formula
Quantity of electrical charge (C) = current (A) x time (s)
Q=Ixt
If we consider the electrical charge as 1 mole of electrons we can then relate this to

moles since 1 mole electrons = 6.02 x 1023 electrons. The charge on one electron is 1.6
x10-19C therefore 1 mol of electrons will have a total charge of 96500 C. this value is

called Faraday’s Constant.

96500C = 1 Faraday

M+ + e-  M
1 mole of cation with a single positive charge will require 1 mole of electrons to be
discharged to form 1 mole M atoms. Which is the same as saying 1 mole of M+ ions
require 96500C (or 1 Faraday) to be discharged.
X2+ + 2e-  X
Y3+ + 3e-  Y

Faraday’s first law- the mass of a substance (or volume of gas) produced at or dissolved
from an electrode during electrolysis is proportional to the quantity of electricity passing
through the electrolyte.
Molar mass = mass of 1 mole of substance

Example
Calculate the mass of lead produced at the cathode when a current of 5.0A flows
through molten lead (ii) bromide for 16 minutes 5 seconds

Quantity of electricity:
Time = 16min 5s = 5+ 16*60 =5+960 = 965s
Q = 5.0A x 965s = 4825 C
Pb 2+ + 2e-  Pb
From the eq. 2 moles of electrons are need to discharge Pb2+ and for 1 mole of Pb
Therefore 2* 96500 C is needed to discharge Pb2+ to form 1 mol Pb
193000 C are required to form 1 mole of Pb
1C would form 1/193000 mol Pb and thus
4825C ÷ 193000C/mol = 0.025 mol Pb
4825C formed 0.025 mol of Pb
1 mole of Pb has a mass of = 207g/mol
Mass of 0.025 mol Pb = 0.025mol * 207 g/mol
= 5.175g
5.175g of Pb are produced at the cathode.
Example
If an electric current of 2.5A is passed through dilute sulphuric acid for 2 hours 34

minutes and 24 seconds, calculate the volume of oxygen produced at the anode at rtp.

Equation for the reaction at the anode:

Vm at rtp = 24 L/mol
Solution
Q=I*t
t= 2*60*60+34*60+24 = 9264s

Q = 2.5A * 9264s =23160 C

4 moles of e- are lost to form 1 mole oxygen

4 * 96500C form 1 mol oxygen; i.e 386000C form 1 mol oxygen

So 23160C will form:

23160C ÷ 386000 C/mol = 0.06 mol of oxygen

1 mol O2 at rtp has a volume of 24L

0.06 mol O2 will have a volume:

0.06 mol * 24 L/mol =1.44 L or 1.44 dm3