10.

ELECTROCHEMICAL CELLS
An electrochemical cell
 Is one that can convert chemical energy into electrical energy. The process
involves a redox reaction.
Reduction: Is the addition of electrons
Oxidation: Is the removal of electrons
 A typical electrochemical cell consists of two separate half cells in which
reduction or oxidation occurs.

Half-cell
 Each half cell consists of a metal electrode dipping in a solution of its own ions.
The two solutions are connected to each other using a salt bridge (a strip of filter
paper soaked in potassium chloride or nitrate solution), or a porous partition.
 The metal electrode is called the;

Anode
 if it’s where oxidation is taking place. That is; it’s where the loss of electrons is
occurring from. The anode is also the negative terminal (electrode) and according
to the cell conversion, it is always placed on the left.

Cathode
 if it’s where reduction is taking place. That is, its where addition of electrons is
occurring from. The cathode is also the positive terminal (electrode) and
according to the cell conversion, it is always placed on the right
 The two electrodes are connected to each other via a wire across a load or
voltmeter.

Diagram of a typical electrochemical cell (the Daniell cell)

Voltmeter

Zinc electrode Salt bridge Copper electrode

Zinc sulphate Copper(II)

solution sulphate solution

Action of an electrochemical cell

 At the anode, the zinc rod dissolves in the solution, leaving two electrons on the
plate.

𝑍𝑛(𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 −

PHYSICAL CHEMISTRY NOTES Page 1 of 9 Ssekyejwe A. Ronald

  These electrons then pass through the wire to the copper terminal which is the
cathode. At this plate, the copper ions in the solution accept the two electrons to
form solid copper

𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)

 The transfer of electrons from the zinc plate to the copper constitutes electricity
and by convention, current will flow in the opposite direction.
 The salt bridge or porous partition serves to complete the circuit by allowing the
movement of ions from one electrolyte to another without the two electrolytes
necessarily mixing
 The working of an electrochemical cell is possible because the two metals
involved have different electrode potentials. In this example zinc has a more
negative electrode potential than copper. Zinc has a higher tendency to loose
electrons compared to copper.

The electrochemical series

 By arranging the elements and their ions in order of their electrode potentials,
an electrochemical series of the different elements is obtained. Part of the series
is given below,

Half-cell reaction Standard electrode potential

(E/V)
𝐿𝑖 + (𝑎𝑞)/𝐿𝑖(𝑠) −3.04
𝐾 + (𝑎𝑞)/𝐾(𝑠) −2.92
𝐶𝑎2+ (𝑎𝑞)/𝐶𝑎(𝑠) −2.87
𝑁𝑎 + (𝑎𝑞)/𝑁𝑎(𝑠) −2.71
𝑀𝑔2+ (𝑎𝑞)/𝑀𝑔(𝑠) −2.37
𝐴𝑙 3+ (𝑎𝑞)/𝐴𝑙(𝑠) Type equation here.
𝑍𝑛2+ (𝑎𝑞)/𝑍𝑛(𝑠)
𝐹𝑒 2+ (𝑎𝑞)/𝐹𝑒(𝑠)
𝑆𝑛2+ (𝑎𝑞)/𝑆𝑛(𝑠)
2𝐻 + (𝑎𝑞)/𝐻2 (𝑔)
𝐶𝑢2+ (𝑎𝑞)/𝐶𝑢(𝑠)
𝐼2 (𝑔)/2𝐼 − (𝑎𝑞)
𝐴𝑔+ (𝑎𝑞)/𝐴𝑔(𝑠)
𝐵𝑟2 (𝑔)/2𝐵𝑟 − (𝑎𝑞)
𝐶𝑙2 (𝑔)/2𝐶𝑙 − (𝑎𝑞)
𝐹2 (𝑔)/2𝐹 − (𝑎𝑞)

Notes from the series

 Electrode potentials are important because they express the relative tendencies
of the elements in their normal states to form hydrated ions in solution
 The order in which the metals occur doesn’t correspond exactly with the order
given by the ionization energies. Thus lithium, which is at the top of the series,
is usually regarded as the least electropositive alkali metal because it has the
highest ionization energy. Lithium owes its high position in the series to the
small ionic radius of its ion. Li+ being the smallest of the alkali metal ions. For
this reason, it becomes the most heavily hydrated in solution and a
correspondingly large amount of energy is evolved. Similarly, calcium occurs

PHYSICAL CHEMISTRY NOTES Page 2 of 9 Ssekyejwe A. Ronald

 above sodium because the double charge on the calcium ion causes greater
hydration of the ion.

 The values of electrode potentials are used to tell the most oxidizing and
reducing agent. For example, the electrode potential of zinc and copper are
-0.76V and +0.34. This implies that zinc ionizes more readily then hydrogen
(0.00V) and hydrogen ionizes more readily than copper. Hydrogen is the
reference electrode.
 The more negative the electrode potential, the stronger the reducing agent and
the more positive the electrode potential, the stronger the oxidizing agent. Hence
lithium is the strongest reducing agent while fluorine is strongest oxidizing
agent.

Measurement of standard electrode potentials

 The standard electrode potential of an element or any other chemical species

cannot be measured absolutely. This is because, it is necessary to have a second
electrode which also has a potential difference with respect to the liquid.

 Hence the values of standard electrode potentials are relative to the standard
hydrogen electrode. The hydrogen electrode is used as the second electrode,
whose electrode potential is arbitrary taken as zero (0.00V). Hence when any
other electrode is connected to the hydrogen electrode, the e.m.f measured is
taken as the standard electrode potential of the specimen electrode.

The standard hydrogen electrode (half -cell)

 The standard hydrogen electrode consists of platinized platinum electrode
dipping in a solution of 1M hydrogen ions, with hydrogen gas bubbling over it at
a temperature of 298K and a pressure of 1atm.
 Platinum is the metal of choice because under these conditions, it is inert. It
also catalyzes the reaction between the hydrogen molecules and the ions.

Diagram of the standard hydrogen electrode

Hydrogen gas at 1 atm

and 298K

Platinum plate

1 M 𝐻 + (𝑎𝑞)

PHYSICAL CHEMISTRY NOTES Page 3 of 9 Ssekyejwe A. Ronald

 Measuring the standard electrode potential of a metal.
Diagram Voltmeter

Hydrogen gas at
1 atm and 298K
Salt bridge Metal electrode
Platinum plate

1M metal ion
1 M 𝐻 + (𝑎𝑞) solution

Procedure
 The metal whose electrode potential is to be measured is dipped in an aqueous
solution of 1M of its ions
 The metal half-cell is placed next to the standard hydrogen half-cell, with
pressure being 1atm and temperature 298K
 The two solutions are connected using a salt bridge. (a strip of filter paper
soaked in a saturated solution of potassium chloride)
 The two electrode plates are then connected using a wire across a high
resistance value voltmeter.
 The reading of the voltmeter is the e.m.f of the specimen half-cell (the electrode
potential of the metal electrode) since that of the hydrogen half-cell is arbitrary
taken as zero.

 Measuring the standard electrode potential of a non-metal e.g. chlorine

Diagram

Voltmeter

Hydrogen gas at Chlorine gas at 1

1 atm and 298K atm and 298K
Salt bridge
Platinum plate Platinum plate

1M 𝐻 + (𝑎𝑞) 1M 𝐶𝑙 − (𝑎𝑞)

Procedure
 A standard chlorine half-cell is made by dipping a platinized platinum plate in a
solution of 1M chloride ions (sodium chloride) and bubbling chlorine gas over it
at 1atm and 298K.

PHYSICAL CHEMISTRY NOTES Page 4 of 9 Ssekyejwe A. Ronald

  Place the chlorine electrode next to the standard hydrogen electrode.
 Connect the two solutions with an electrolyte salt bridge
 Connect the two plates of the half-cells using a wire across a high resistance
value voltmeter.
 The reading of the voltmeter is taken as the standard electrode potential of the
chlorine electrode.

Standard electrode potential:

 Is the potential difference between a standard hydrogen half-cell and a half cell of
the electrode containing a solution of 1 molar of its ions at temperature of 298K
and 1 atmosphere pressure.
OR
 Is the reduction potential of an electrode obtained with reference to a standard
hydrogen electrode when the electrode is dipping in a solution of 1 molar of its
ions at temperature of 298K and 1atmosphere pressure.

Factors affecting the values of electrode potential of a metal electrode

1. Sublimation/ atomization energy:

 Sublimation is an endothermic process. The higher the atomization energy the
lower is the negative value of electrode potential. This is because it is more
difficult to convert the element into gaseous atoms.

2. Ionization energy:
 Ionization of a metal is an endothermic process. The higher the ionization
energy, the lower is the negative value of electrode potential. This is because it is
more difficult to convert the gaseous atoms into ions.

3. Hydration energy:
 Hydration of ions is an exothermic process. The higher the hydration energy,
the higher is the negative value of electrode potential. This is because it is
easier to convert the gaseous ions into the aqueous ions

Other factors include

 Concentration
 Temperature
 Pressure

Arrangement of cells, the cell notation and cell e.m.f

 If a cell is constructed from two different half cells, the positive pole of the cell is
placed on the right, while the negative pole on the left by convention.
 The resultant e.m.f of the cell, (𝑬𝜽 (𝒄𝒆𝒍𝒍)) can be obtained by subtracting the
reduction electrode potentials of the half-cells algebraically from the formula.

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = 𝐸 𝜃 (𝑟𝑖𝑔ℎ𝑡) − 𝐸 𝜃 (𝑙𝑒𝑓𝑡)

𝑂𝑅

PHYSICAL CHEMISTRY NOTES Page 5 of 9 Ssekyejwe A. Ronald

 𝐸 𝜃 (𝑐𝑒𝑙𝑙) = 𝐸 𝜃 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸 𝜃 (𝑎𝑛𝑜𝑑𝑒)

Provided, the two electrode potentials given are reduction potentials.

 The negative pole (anode) on the left is electron donor and is the half-cell with a
more negative (less positive) reduction potential.
 The positive pole (cathode) on the right is electron acceptor and is the half-cell
with less negative (more positive) reduction potential.
 The cell notation is a shorthand way of expressing a certain reaction in an
electrochemical cell.

Example I
The electrode potentials of the zinc and copper half cells are given below

𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠); 𝐸 𝜃 = +0.34V

𝑍𝑛2+ (𝑎𝑞) + 2𝑒 − → 𝑍𝑛(𝑠); 𝐸 𝜃 = −0.76V

Write the cell notation/convention and calculate the e.m.f of the cell produced
when the two half cells are combined.

Solution
 Step I: Check whether the half-cell potentials given are reduction potentials (yes;
they are.)
 Step II: identify the half-cell with a more negative potential. (It is the zinc half-
cell). This will constitute the left half of the electrochemical cell. It is the negative
electrode as well as the anode. It’s arranged to produce electrons. i.e. the half-
cell equation at the anode.

𝑍𝑛(𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 − : Equation at the anode

 The half-cell with the more positive electrode potential is the cathode as well as
the positive electrode. It’s to be placed on the right. It’s arranged to accept
electrons. i.e. the half-cell equation at the cathode

𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) : Equation at the cathode

 Step III; write the cell convention (also called cell notation) with the zinc half-cell
on the right and the copper half-cell on the left separated by double vertical lines
to represent the salt bridge. A single vertical line or slash indicates the phase
boundary.
i. The notation: 𝑍𝑛(𝑠)⁄𝑍𝑛2+ (𝑎𝑞) ‖ 𝐶𝑢 2+ (𝑎𝑞)⁄𝐶𝑢 (𝑠)

e.m.f of the cell:

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = 𝐸 𝜃 (𝑟𝑖𝑔ℎ𝑡) − 𝐸 𝜃 (𝑙𝑒𝑓𝑡)

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = +0.34 −− 0.76

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = +1.10𝑉

PHYSICAL CHEMISTRY NOTES Page 6 of 9 Ssekyejwe A. Ronald

  The overall cell reaction can be obtained by combining the two half-cell
equations. E.g.

𝑍𝑛(𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 −

𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠)

Overall: 𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝐶𝑢(𝑠) + 𝑍𝑛2+ (𝑎𝑞)

Example II
The electrode potentials of two half-cells are given below

𝐹𝑒(𝑠)/𝐹𝑒 2+ (𝑎𝑞) 𝐸 𝜃 = +0.44V

𝑆𝑛(𝑠)/𝑆𝑛2+ (𝑎𝑞) 𝐸 𝜃 = +0.14V

i. Write the cell notation of the cell formed from the two half-cells
ii. Calculate the e.m.f of the cell formed from the two half-cells

Solution
 Step I: Check whether the electrode potentials given are reduction potentials No;
they are not)
 Step II: Change the half-cells reactions to reduction and change the signs of the
electrode potentials

𝐹𝑒 2+ (𝑎𝑞)/𝐹𝑒(𝑠) 𝐸𝜃 = -0.44V

𝑆𝑛2+ (𝑎𝑞)/𝑆𝑛(𝑠) 𝐸𝜃 = -0.14V

 Step III: Identify the half-cell with a more negative electrode potential. This
constitutes the anode (left of the cell) and it should be arranged such that it
produces electrons.
 The iron half-cell will be the anode; however, it must be written in such a way that
it is producing electrons. (i.e. oxidation should be occurring at this terminal)

𝐹𝑒(𝑠)/𝐹𝑒 2+ (𝑎𝑞) – This is oxidation

 The tin half-cell is the cathode and it should be written such that electrons are
accepted. (Reduction should be occurring at this terminal)

𝑆𝑛2+ (𝑎𝑞)/𝑆𝑛(𝑠) – This is reduction

i. the cell notation

𝐹𝑒(𝑠)/𝐹𝑒 2+ (𝑎𝑞) ‖ 𝑆𝑛2+ (𝑎𝑞)/𝑆𝑛(𝑠)

ii. e.m.f of the cell

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = 𝐸 𝜃 (𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸 𝜃 (𝑎𝑛𝑜𝑑𝑒)

PHYSICAL CHEMISTRY NOTES Page 7 of 9 Ssekyejwe A. Ronald

 𝐸 𝜃 (𝑐𝑒𝑙𝑙) = −0.14 −− 0.44

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = +0.30𝑉

The use of inert electrodes

 If a half-cell is set up with a non-metal electrode, then an inert electrode is
dipped in a solution of the ions of the non-metal to provide a surface over which
the reactions can take place.
 An inert electrode is also used in case the half-cell reactions occur between
particles in solution. For example, iron exists either as Fe(II) or Fe(III). In an
aqueous solution containing both Fe(II) and Fe(III) ions, there is a tendency of
Fe(II) ions to lose electrons and Fe(III) to gain them.

Example I:
The electrode potentials of some half-cells are given below.

𝐹𝑒 3+ (𝑎𝑞), 𝐹𝑒 2+ (𝑎𝑞) 𝐸 𝜃 = −0.77𝑉

𝑆𝑛4+ (𝑎𝑞), 𝑆𝑛2+ (𝑎𝑞) 𝐸 𝜃 = +0.15𝑉

i. write the cell notation for the combined half-cells

ii. calculate the e.m.f of the cell formed from the half-cells

Solution
 Since the transfer of electrons is occurring in between particles in solution, then
an inert electrode (platinum) is to be used.
 Note that, in each half-cell, the transfer of electrons is occurring between species
in the same phase (aqueous) and a comma (,) is used to separate these chemical
species.

i. 𝑃𝑡(𝑠)/𝐹𝑒 2+ (𝑎𝑞), 𝐹𝑒 3+ (𝑎𝑞) ‖ 𝑆𝑛4+ (𝑎𝑞), 𝑆𝑛2+ (𝑎𝑞)/𝑃𝑡(𝑠)

ii. 𝐸 𝜃 (𝑐𝑒𝑙𝑙) = 𝐸 𝜃 (𝑟𝑖𝑔ℎ𝑡) − 𝐸 𝜃 (𝑙𝑒𝑓𝑡)

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = +0.15 −− 0.77

𝐸 𝜃 (𝑐𝑒𝑙𝑙) = +0.92𝑉

Example II
 The electrode potentials of some half-cells are given below.

𝐶𝑙2 (𝑔)/2𝐶𝑙 − (𝑎𝑞) 𝐸 𝜃 = +1.36𝑉

𝐹𝑒 3+ (𝑎𝑞), 𝐹𝑒 2+ (𝑎𝑞) 𝐸 𝜃 = −0.77𝑉

i. write the cell notation for the combined half-cells

ii. calculate the e.m.f of the cell formed from the half-cells

PHYSICAL CHEMISTRY NOTES Page 8 of 9 Ssekyejwe A. Ronald

 Solution
i. 𝑃𝑡(𝑠)/𝐹𝑒 2+ (𝑎𝑞), 𝐹𝑒 3+ (𝑎𝑞) ‖𝐶𝑙2 (𝑔), 𝐶𝑙 − (𝑎𝑞)/ 𝑃𝑡(𝑠).

ii. 𝐸 𝜃 (𝑐𝑒𝑙𝑙) = +2.13𝑉

Feasibility of cells
The feasibility of a cell (or being spontaneous) can be deduced from
 e.m.f of the cell: when this is positive, the cell is feasible and when it is negative,
the cell is not feasible.
Not being feasible implies that the reactions shown cannot take place/ not
possible.

 Free energy of the cell: the energy produced by the cell, ∆𝑮 also called Gibbs free
energy, can be calculated from the formula, ∆𝑮 = −𝒏𝑭𝑬𝜽 , where,

𝒏 ≡ 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏𝒔 𝒊𝒏𝒗𝒐𝒍𝒗𝒆𝒅 𝒊𝒏 𝒂 𝒃𝒂𝒍𝒂𝒏𝒄𝒆𝒅 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏

𝑭 ≡ 𝑭𝒂𝒓𝒂𝒅𝒂𝒚′ 𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 (96500C)
𝑬𝜽 ≡ 𝒆. 𝒎. 𝒇 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒆𝒍𝒍 𝒄𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒆𝒅
example
Determine the free energy produced from the cell

𝑃𝑡(𝑠)/𝐹𝑒 2+ (𝑎𝑞), 𝐹𝑒 3+ (𝑎𝑞) ‖ 𝐶𝑙2 (𝑔), 𝐶𝑙 − (𝑎𝑞)/𝑃𝑡(𝑠)

whose e.m.f. is +2.13V

solution

2𝐹𝑒 2+ (𝑎𝑞) → 2𝐹𝑒 3+ (𝑎𝑞) + 2𝑒 −

𝐶𝑙2 (𝑔) + 2𝑒 − → 2𝐶𝑙 − (𝑎𝑞)

2𝐹𝑒 2+ (𝑎𝑞) + 𝐶𝑙2 (𝑔) → 2𝐹𝑒 3+ (𝑎𝑞) + 2𝐶𝑙 − (𝑎𝑞)

From ∆𝐺 = −𝑛𝐹𝐸 𝜃

𝑛 = 2 (electrons in balanced reaction)

𝐹 = 96500𝐶

𝐸 𝜃 = +2.13𝑉

∆𝐺 = −2 × 96500 × 2.13

∆𝐺 = −411090 J

PHYSICAL CHEMISTRY NOTES Page 9 of 9 Ssekyejwe A. Ronald