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Electrochemistry

Measurement of pH

- Measurement of pH can be by electrochemical method using the pH meter or by

colorimetric method which involves the use of universal pH indicator paper or universal
indicator solution and pH chart. Colorimetric method lacks precision. A universal indicator
is a mixture of pH sensitive dyes. Measurement of pH is more accurate when a calibrated
pH meter is used.
Sensitive - The pH of a solution is most easily
voltmeter measured potentiometrically. A glass
Calomel electrode electrode which is sensitive to hydrogen
Glass (reference electrode)
electrode ions (H+) concentration is dipped into a
Mercury (Hg)
Hg2Cl2 saturated
test solution with a saturated calomel as
with KCl(aq) the reference electrode to form a cell.
Porous plug When the electrodes are dipped into a test
solution a voltage is generated between the
Test solution
acid in the glass bulb and the acid solution
outside the glass bulb. The voltage is then converted directly to a pH value by the pH meter.
The glass electrode is filled acid of known concentration hence and known pH.

Definition: A pH meter is an electronic device which when calibrated gives the pH value of a
solution directly.

- In order to calibrate a pH meter, its electrodes are immersed into a buffer solution of
known pH and the pH meter reading adjusted to the value corresponding to the pH of the
buffer solution.
-
The rusting of iron
Rusting is and electrochemical process and has a yearly cost worldwide which can only be
estimated in billions. Rust is hydrated iron (III) oxide with the general formula, Fe 2O3.xH2O
where x = 1 or 2 in a number of cases. Rusting is a redox reaction that occurs when both
water and oxygen are present. The corrosion starts with the oxidation of iron to Fe2+ at the
anode.
Fe(s) → Fe2+(aq) + 2e-;
Electrons released travel through the iron metal until they get to the cathode and reduce the
dissolved oxygen in water to hydroxide ions.
O2(aq) + 2H2O(l) + 4e- → 4OH-(aq) ; Eθ = +1.23V.
The Fe2+ migrate through the water to the cathode and combine with OH- ions to form iron
(II) hydroxide precipitate;
Fe2+(aq) + 2OH-(aq) → Fe(OH)2(s).
The Fe(OH)2(s) undergoes oxidisation to iron (III) hydroxide; Fe(OH)3(s).
Fe(OH)2(s) + ½O2(g) → Fe(OH)3(s).
The Fe(OH)3(s) then partially dehydrates to give rust, Fe2O3.xH2O which is flaky reddish
brown solid. Thus the equation for the partial dehydration of iron (III) hydroxide to form
rust depends on the number of molecules of crystallisation retained by iron (III) oxide.

2Fe(OH)3(s) → Fe2O3.H2O(s) + 2H2O(l). OR

2Fe(OH)3(s) → Fe2O3.2H2O(s) + H2O(l).

The equation below is the overall equation for the formation of rust.
4Fe(s) + 3O2(aq) + 2xH2O(l) → 2Fe2O3.xH2O(s).
Any equation for rusting contains oxygen in the aqueous state and not the gaseous state
because it is dissolved oxygen in water that takes part in the rusting process.

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N
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Electrochemistry

Factors affecting rusting of iron

- The presence of air and moisture to act as anode.

- Presence of hydrogen ions.
- The presence of less reactive metals such as Sn, Cu etc as impurities
- The presence of a strain
- The presence of certain salt solutions e.g. NaCl which are catalytic in their action
-
Preventing rust

Coating the Iron: By adding a layer of paint, oil or grease to the iron, you prevent oxygen
and water from coming into contact with the iron.
Sacrificial Protection: A most effective way of preventing rust is to coat the iron with zinc,
this is called galvanisation. It works due to zinc's greater reactivity, i.e. zinc has a greater
tendency to lose electrons and form ions, hence any Fe2+ present are reduced to Fe atoms.
Alloying: Iron can be alloyed with nickel, chromium or carbon. The presence of other
elements helps prevent Fe2+ forming and electrons been released, hence preventing the
rusting process starting.

Act:
Given the piece of iron bar below with a drop of water on it for rusting to occur.
Drop of water (a) What is rust?
(b) What is present in the drop of water that without it there
will be no rusting?
Iron bar (c) Rusting is an electrochemical process.

(i) Which part of the diagram is the anode?

(ii) Which part of the diagram is the cathode?
(d) Given the following half-cells involved in the rusting of iron.
Fe2+(aq) + 2e- → Fe(s); Eθ = - 0.44V
- -
O2(g) + 2H2O(l) + 4e → 4OH (aq) ; Eθ = +1.23V
Considering the two half equations of an electrochemical cell,
(i) Calculate the emf of the cell.
(ii) Write a cell notation diagram for the cell.
(iii) Write down an equation for the reaction that takes place in the cell.
(e)

THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N