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INSTITUTE OF HEALTH SCIENCES AND NURSING

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PRACTICE EXERCISE 5
CHAPTER 5: Fundamentals of Electrochemistry

GROUP 5
ACABADO, LOVELY MONETTE B.
BERNALES, AIZHA JERRICA L.
CRUZ, AISHA GRACHELLA S.
TORRES, SAM GABRIEN V.
ZINAMPAN, ALLIAH ZYRILE C.

Electrochemistry

Electrochemistry is the branch of chemistry that deal with the interconversion of electrical
energy and chemical energy. Electrochemical processes are redox reaction* in which the energy
released by spontaneous reaction is converted to electricity, or in which electrical energy Is used
to cause a nonspontaneous reaction to occur (spontaneity of a reaction will be discussed under
Cell Potential).

Redox (Reduction-Oxidation) Reactions*

-reactions where electrons are transferred from one species to another. In redox reactions, two
separate reactions occur simultaneously as two half-reactions:
• Reduction reactions are reactions where electrons are gained by the species.
Ex: 𝐴𝑔+ (𝑎𝑞) + 𝑒 − → 𝐴𝑔(𝑠)

• Oxidation reactions are reactions where electrons are given off by the species.
Ex: 𝐶𝑢(𝑠) → 𝐶𝑢2+ (𝑎𝑞) + 2𝑒 −

(Balancing of redox reactions is discussed further in your laboratory session)

Electrochemical Cell
An electrochemical cell is a system consisting of electrodes that dip into an electrolyte and in
which a chemical reaction either uses or generates an electric current.
 • A voltaic, or galvanic, cell is an electrochemical cell in which a spontaneous reaction
generates an electric current.
• An electrolytic cell is an electrochemical cell in which an electric current drives an
otherwise nonspontaneous reaction.

An electrochemical cell is usually composed of three components:

• An electrode is a solid platform used to make electrical contact with a non-metallic part
of the circuit. Electrodes are usually metallic but there are non-metallic ones like carbon
rods.
o An anode refers to the electrode where oxidation occurs (An Ox).
o A cathode refers to the electrode where reduction occurs (Red Cat).
• Electrolyte solution, which could be an aqueous solution containing dissolved ions or
liquid amalgam that can conduct electricity.
• A salt bridge which is a tube on an electrolyte in a gel that connects the two half-cells of
a voltaic cell; the salt bridge allows the flow of ions but prevents the mixing of the
different solutions that would allow direct reaction of the cell reactants.

Rather than drawing the electrochemical cell’s complete diagram, it is simply written using the
cell notation, wherein the cell’s anode is written first, followed by the salt bridge, then the cell’s
cathode.

Cell Notation: anode | anode | (salt bridge) | cathode| cathode

The components of the cell are written in order, starting with the left-hand and moving across
the salt bridge to the right. A single vertical line indicates a phase boundary, such as that
between the electrode and its ionic counterpart. The double vertical line represents a salt
bridge. Spectator ions are usually omitted.
Ex: 𝐶𝑢 | 𝐶𝑢2+ (1.0 𝑀)|| 𝑍𝑛2+ (1.0 𝑀) | 𝑍𝑛

In the example above, the anode is the Cu, while the cathode is Zn. Note that electrodes must be solid
platforms, and that ions actually are part of the redox reactions happening in the cell’s electrode. Single bar
indicate the electrode’s boundary with the solution while double bar indicate salt bridge.

Cell Potential and Standard Reduction Potential

An electrochemical cell’s electrical

energy is measured using the quantity
cell potential (Ecell). Specifically, it is the
measure of the potential difference
between two half cells in an
electrochemical cell. The potential
difference is caused by the ability of
electrons to flow from one half cell to the
other.

The cell’s standard potential is measured

as the difference between the standard
cell potential of the cathode and the
anode. We denote standard cell potential
as E°cell (take note that the E°cell is read as
E naught cell and the ° indicates that the
quantity is a standard quantity).

𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸°𝑎𝑛𝑜𝑑𝑒

The cell’s standard potential is

determined by looking on the Table of
Standard Reduction Potentials (on the
right). The more positive the reduction
potential, the stronger it is as an
oxidizing agent (GE R OA). The more
negative the reduction potential, the
stronger it is as an reducing agent (LE O
RA).

Standard Hydrogen Electrode (SHE)

Take a look at the half-reaction 2𝐻 + (𝑎𝑞) + 2𝑒 − → 𝐻2(𝑔) . It has the E°cell = 0.00V. Actually, this has
a value. However, the value was made to zero because it serves as the basis to calculate cell
potentials using different electrodes or different concentrations. This half reaction is what you call
as Standard Hydrogen Electrode (SHE). SHE actually is the basis for the standard reduction
potentials found in the table above.

Nernst Equation

All of the standard reduction potentials are measured under the following conditions:
• Reaction is in equilibrium (no further reactions taking place).
• Concentrations of dissolved species in each half-reaction is 1.0 M, while pressure is 1.0
atm.
• Temperature of 298 K (25°C) and atmospheric pressure of 1 bar.

Should any of these conditions change, the cell now has a nonstandard cell potential.

If the electrochemical cell is under nonstandard conditions, the E cell is actually solved using the
Nernst equation:
𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − ln 𝑄
𝑛𝑒 − ℱ

0.0592
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − log 𝑄
𝑛𝑒 −

Where: 𝐸°𝑐𝑒𝑙𝑙 = 𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐶𝑒𝑙𝑙 𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙

[𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
𝑄 = [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
𝑛𝑒 − = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛𝑣𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑤ℎ𝑜𝑙𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

Take note that for a half-cell’s Nernst equation, it should be in reduced form!
If the reaction is at equilibrium, the Ecell is equal to 0, thus:

0.0592
𝐸°𝑐𝑒𝑙𝑙 = log 𝐾
𝑛𝑒 −

Worked Example
Consider the half-cell below:

𝑃𝑡| 𝑁𝑂(𝑔) (0.45 𝑎𝑡𝑚), 𝐻𝑁𝑂3(𝑎𝑞) (0.2𝑀)

Anode Platinum wire

Reaction at anode 𝑁𝑂(𝑔) + 2𝐻2 𝑂(𝑙) → 𝑁𝑂3 − (𝑎𝑞) + 4𝐻+ (𝑎𝑞) + 3𝑒 −

E°cell (V) 0.96 V Ecell (V) 0.90 V

 Solution:
If half-cell, reaction must be in reduction form! The reduction half-reaction is given as:

𝑁𝑂3 − (𝑎𝑞) + 4𝐻+ (𝑎𝑞) + 3𝑒 − → 𝑁𝑂(𝑔) + 2𝐻2 𝑂(𝑙)

Using the Nernst Equation:

0.0592
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − log 𝑄
𝑛𝑒 −

𝑃𝑁𝑂 0.45
𝐸°𝑐𝑒𝑙𝑙 = 0.96 𝑉; then 𝑄 = [𝑁𝑂 − + 4 = (0.2)(0.2)4 = 1406.25
3 ][𝐻 ]
𝑛𝑒 − = 3𝑒 − , 𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑡ℎ𝑒 𝑟𝑒𝑑𝑜𝑥 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑎𝑏𝑜𝑣𝑒

0.0592
𝐸𝑐𝑒𝑙𝑙 = 0.96 𝑉 − [ log(1406.25)]
3
𝐸𝑐𝑒𝑙𝑙 = 0.90 𝑉

Consider the electrochemical cell below:

𝑍𝑛|𝑍𝑛2+ (0.1𝑀)||𝐴𝑔𝐶𝑙, 𝐶𝑙− (0.05𝑀)| 𝐴𝑔

Cathode silver-silver chloride electrode Anode zinc electrode

Reaction at Reaction at
𝐴𝑔(𝑠) + 𝐶𝑙− (𝑎𝑞) + 𝑒 − → 𝐴𝑔𝐶𝑙(𝑠) 𝑍𝑛(𝑠) → 𝑍𝑛 2+ (𝑎𝑞) + 2𝑒 −
cathode anode
E°cell (V) 0.98 V Ecell (V) 0.93 V
Solution:
For E°cell:
𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸°𝑎𝑛𝑜𝑑𝑒
𝐸°𝑐𝑒𝑙𝑙 = 0.22 𝑉 − (−0.76 𝑉 ) = 0.98 𝑉
For Ecell:
1.The equation is:
𝑍𝑛(𝑠) + 2𝐴𝑔(𝑠) + 2𝐶𝑙 − (𝑎𝑞) → 2𝐴𝑔𝐶𝑙(𝑠) + 𝑍𝑛 2+ (𝑎𝑞)

Using the Nernst Equation:

0.0592
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − log 𝑄
𝑛𝑒 −

[𝑍𝑛 2+ ] 0.1
𝐸°𝑐𝑒𝑙𝑙 = 0.98 𝑉; then 𝑄 = [𝐶𝑙− ]2
= (0.05)2 = 40
 𝑛𝑒 − = 2𝑒 − , 𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑡ℎ𝑒 𝑟𝑒𝑑𝑜𝑥 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑎𝑏𝑜𝑣𝑒

0.0592
𝐸𝑐𝑒𝑙𝑙 = 0.98 𝑉 − [ log(40)]
2
𝐸𝑐𝑒𝑙𝑙 = 0.93 𝑉

Gibbs Free Energy and Cell Potential

Electrochemistry deals with interconversion of electrical energy and chemical energy. With this
conversion, we can either use spontaneous reactions to supply electrical energy, or use electric
currents to drive nonspontaneous reactions.

What are spontaneous and non-spontaneous reactions?

• Spontaneous reactions are chemical reactions which proceed naturally, without
requirement of energy. Spontaneous reactions are always accompanied by release of
energy.
• Nonspontaneous reactions require energy for it to occur and proceed into completion.
Spontaneous reactions can provide energy for nonspontaneous reactions.

The spontaneity of a chemical reaction, including redox reactions can be measured using Gibbs
free energy (ΔG). (The exact definition of Gibbs free energy is actually a long-winded solution
involving calculus and thermodynamics, so just accept the definition above). Gibbs free energy
can predict the direction of a reaction (spontaneity) based on the sign.

We can solve Gibbs free energy as:

∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝑄
Where R = 8.314 J/mol•K

However at standard conditions, that is, reaction is at equilibrium, ΔG is actually equal to 0.

Therefore,

∆𝐺° = −𝑅𝑇 ln 𝐾

Another way to solve ΔG is using the equation below. Note that this time, the equation is in terms
of Ecell. Take note of the °, which means standard value

∆𝐺° = −𝑛𝑒 ℱ𝐸°𝑐𝑒𝑙𝑙

∆𝐺 = −𝑛𝑒 ℱ𝐸𝑐𝑒𝑙𝑙

Where: ℱ = 96 500 𝐶⁄𝑚𝑜𝑙 • 𝐾

To summarize, at STANDARD CONDITIONS (T=298 K; reaction at equilibrium or K):

0.0592
𝐸°𝑐𝑒𝑙𝑙 = log 𝐾 (𝐸𝑞𝑛 1)
𝑛𝑒 −

∆𝐺° = −𝑛𝑒 ℱ𝐸°𝑐𝑒𝑙𝑙 (𝐸𝑞𝑛 2)

∆𝐺° = −𝑅𝑇 ln 𝐾 (𝐸𝑞𝑛 3)

We can solve for the equilibrium constant K by equating Eqn 2 and Eqn 3.

𝑅𝑇 ln 𝐾 = 𝑛𝑒 ℱ𝐸°𝑐𝑒𝑙𝑙

𝑛𝑒 ℱ𝐸°𝑐𝑒𝑙𝑙
ln 𝐾 =
𝑅𝑇
𝑛𝑒 ℱ𝐸°𝑐𝑒𝑙𝑙
𝐾=𝑒 𝑅𝑇

Redox Titration (Potentiometric)

Compared to acid-base titration where the titration is monitored by the pH of the solution upon
the addition of titrant, in redox titration, the Ecell are monitored.

Solution Equation for 𝑬𝒄𝒆𝒍𝒍 for 1:1 electron

Stage Equation for Q
Composition ratio

Initial No equation

Pre- 0.0592 𝑀𝐴 𝑉𝐴 − 𝑀𝑇 𝑉𝑇
Mostly analyte 𝐸𝐴 = 𝐸𝐴𝑜 − log 𝑄 𝑄=
Equivalence 𝑛𝑒 𝑀𝑇 𝑉𝑇

All are 𝑜 𝑜 A and B are the stoich

Equivalence 2𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐴𝐸𝑎𝑛𝑎𝑙𝑦𝑡𝑒 + 𝐵𝐸𝑡𝑖𝑡𝑟𝑎𝑛𝑡
equivalent coefficients

Post- 0.0592 𝑀𝑇 𝑉𝑇
Mostly titrant 𝐸𝑇 = 𝐸𝑇𝑜 − log 𝑄 𝑄=
Equivalence 𝑛𝑒 𝑀𝑇 𝑉𝑇 − 𝑀𝐴 𝑉𝐴
Worked Example:

A 50 mL solution of 0.100 M Fe 2+ (analyte) was titrated with 0.100 M Ce4+ (titrant) in a matrix of
1M HClO4. Solve for the E(V) when:
First, define the redox reaction:
𝐹𝑒 2+ + 𝐶𝑒 4+ → 𝐹𝑒 3+ + 𝐶𝑒 3+

a. 0.0 mL of titrant added

Since no titrant was added, E= 0.00V

b. 10.0 mL of titrant added

At this point, nanalyte > ntitrant , so this is at pre-equivalence stage. For this part, we use the formula
𝑜 0.0592 𝑀𝐹𝑒 𝑉𝐹𝑒 − 𝑀𝐶𝑒 𝑉𝐶𝑒
𝐸𝐹𝑒 = 𝐸𝐹𝑒 3+ , 𝐹𝑒 2+ − { × log }
1 𝑀𝐶𝑒 𝑉𝐶𝑒

0.0592 (0.1 × 50.0) − (0.1 × 10.0)

𝐸𝐹𝑒 = 0.77 − { × log [ ]}
1 (0.1 × 10.0)

𝐸𝐹𝑒 = 0.73 𝑉

c. 50.0 mL of titrant added

At this point, nanalyte = ntitrant, so this is the equivalence point. You can predict the equivalence point
of by using the formula M1V1 = M2V2.

𝑜 𝑜
2𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = 𝐴𝐸𝑎𝑛𝑎𝑙𝑦𝑡𝑒 + 𝐵𝐸𝑡𝑖𝑡𝑟𝑎𝑛𝑡

𝑜 + 𝐸𝑜
2𝐸 = 𝐸𝐹𝑒 𝐶𝑒

𝑜 + 𝐸𝑜
𝐸𝐹𝑒 𝐶𝑒
𝐸=
2

0.77 𝑉 + 1.61 𝑉
𝐸= = 1.19 𝑉
2

d. 60.0 mL of titrant added

At this point, nanalyte < ntitrant, so this is the post-equivalence point. For this part, we use the formula:

𝑜 0.0592 𝑀𝐶𝑒 𝑉𝐶𝑒

𝐸𝐶𝑒 = 𝐸𝐶𝑒 4+ , 𝐶𝑒 3+ −{ × log }
1 𝑀𝐶𝑒 𝑉𝐶𝑒 − 𝑀𝐹𝑒 𝑉𝐹𝑒

0.0592 (0.1 × 60.0)

𝐸𝐶𝑒 = 1.61 − { × log [ ]}
1 (0.1 × 60.0) − (0.1 × 50.0)

𝐸𝐶𝑒 = 1.56 𝑉
Practice Exercises
Given are electrochemical cells below. Supply the missing information and solve for the E cell (10
points per item).

(CRUZ)

A. 𝐹𝑒|𝐹𝑒 2+ (0.2𝑀)||2𝐼 − (0.03𝑀), 𝐼2 |, 𝑃𝑡

Cathode Iodine-iodine electrode Anode Iron electrode

Reaction at − Reaction at +
2 𝐼𝑎𝑞 → 𝐼2 𝑠 + 2 𝑒 − 𝐹𝑒𝑠 → 𝐹𝑒 2 𝑎𝑞 + 2 𝑒 −
cathode anode
E°cell (V) 0.97 V Ecell (V) 0.94 V
Solution:

𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸°𝑎𝑛𝑜𝑑𝑒

𝐸°𝑐𝑒𝑙𝑙 = (+0.53 𝑉) − (−0.44 𝑉) = 0.97 𝑉

− → 𝐹𝑒 2 + −
𝐹𝑒𝑠 + 2𝐼𝑎𝑞 𝑎𝑞 + 2𝐼2 𝑠 + 4 𝑒

0.0592
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − log 𝑄
𝑛𝑒 −

𝐸°𝑐𝑒𝑙𝑙 = 0.97 𝑉

[𝐹𝑒 2+ ] 0.2
𝑄= = = 222.22
[𝐼 − ]2 (0.03)2

𝑛𝑒 − = 4𝑒 −

0.0592
𝐸𝑐𝑒𝑙𝑙 = 0.97 𝑉 − [ log(222.22)]
4

𝐸𝑐𝑒𝑙𝑙 = 0.94 𝑉
(ACABADO)

C. A 10 mL solution of 0.25 M H2O2 was titrated with 0.1 M KI.

1-3. Give the reduction, oxidation, and overall reaction of the titration process. (BERNALES)
4-6. Predict the equivalence point volume (Veq) of the titration process. (TORRES)

7-10. Calculate the Ecell of the titration system at the equivalence point. (ZINAMPAN)