EKO UNIVERSITY OF MEDICINE AND HEALTH SCIENCES, IJANIKIN, LAGOS

FACULTY OF BASIC MEDICAL SCIENCES

DEPARTMENT OF CHEMISTRY

COURSE TITLE: GENERAL CHEMISTRY II

COURSE CODE: CHM 102
(LECTURE NOTE AND ASSIGNMENT)

BY

ERESANYA .O.I
(M.Sc, PGDE, B.Sc, O.N.D, MCSN, MICCON, MTRCN)
INTRODUCTION TO ELECTROCHEMISTRY

LECTURE 7
A bar of zinc metal (anode) is placed in zinc sulphate solution in the left container. A
bar of copper (cathode) is immersed in copper sulphate solution in the right container.
The zinc and copper electrodes are joined by a copper wire. A salt bridge containing
potassium sulphate solution interconnects the solutions in both the anode and
cathode compartments.
The oxidation half-reaction occurs in the anode compartment.
Zn(s)→ Zn2+(aq) + 2e-

The reducing half-reaction occurs in cathode compartment.

Cu2+(aq) + 2e-→ Cu(s)
The above cell indicates that electrons flow from zinc (anode) through the wire to copper
(cathode). Hence, zinc dissolves from the anode to the solution to form Zn2+ ions. The
Cu2+ ions in the cathode half cell pick up electrons and are converted to Cu atoms on the
cathode.
SO42- ions from the cathode half-cell migrate to the anode half-cell through the salt
bridge. Also, Zn2+ ions from the anode half-cell migrate to the cathode half-cell through
the salt bridge. This flow of ions from one half-cell to the other complete the electrical
circuits which ensures continuous supply of current. The cell will operate until either of
Zn metal or Cu ion is completely used up.
Daniel Cell
It was a typical voltaic cell. It was named after the British chemist, John Daniel. It is a
simple zinc-copper cell like the one described above.

In this cell, the salt-bridge has been replaced by a porous pot. Daniel cell resembles
voltaic cell in all details except that Zn2+ and SO42- ions migrate to the cathode and
anode respectively through the porous pot instead of salt-bridge. In the light of this
difference, the cell diagram remains the same.
Cell Reaction
The flow of electrons from one electrode to the other in an electrochemical cell is
caused by the half-reactions taking place in anode and cathode compartments. The
net chemical change obtained by adding the two half-reactions is called the cell
reaction.
Thus, for a simple voltaic cell described above, we have
(a) Half-reactions:
Zn(s)→ Zn2+(aq) + 2e-

Cu2+(aq) + 2e-→ Cu(s)

(b) Cell reaction by adding up the half reactions:

Zn(s) + Cu2+(aq)→ Zn2+(aq) + Cu(s)
 Cell diagram or Representation of a Cell
This is an abbreviated symbolic depiction of an electrochemical cell.
In 1953, IUPAC recommended the following conventions for writing cell diagrams.
For instance Daniel cell can be represented symbolically as:
Zn(s) / Zn2+(aq) // Cu2+(aq) / Cu(s)
In general, the symbolic representation of an electrochemical cell is;
Anode/Anode electrolyte//Cathode electrolyte/Cathode
Note the following:
(a) The slash line (/) represents the phase boundary between metal electrode and ion
solution (electrolyte).
(b) The double slash lines (//) represent the salt bridge or a porous partition or any other
means of permitting ion flow while preventing electrolyte from mixing.
(c) Each side of the double slash lines (//) represents the half-reaction characters. i.e. anode
half-cell is written on the left hand side and cathode half-cell is written on the right hand
side.
(d) The symbol for an inert electrode, like the platinum electrode is often enclosed in a
bracket.
(e) For an electrochemical cell to produce electricity, the anode element must be more
reactive than the cathode element. That is, the anode element must be higher in the
electromotive series than the cathode element. The rationale for this type of combination
of electrodes is to be able to have spontaneous net reaction occurring in the cell.
Cell Potential or the E.m.f of a cell
The flow of current through the circuit is determined by the ‘push’ of electrons at the
anode and the ‘attraction’ of the electrons at the cathode. These two forces constitute
the ‘driving force’ or ‘electrical pressure’ that send electrons through the circuit.
This driving force is called the electromotive force (e.m.f) or cell potential. The e.m.f is
measured in volts (V) and also referred to as cell voltage.

The standard electromotive force (e.m.f) of a cell (E0cell )

This is a measure of the driving force (e.m.f) with which current flows out of the cell.
It is also called the standard cell potential. E 0cell is also the vigour with which a redox
reaction takes place in the cell when the concentration of electrolytes of electrodes is
1.00 mol dm-3 at 250C.
The sign of standard electromotive force of a cell, E 0cell can be used to predict whether
or not the redox reaction occurring in a cell is feasible. If the E 0cell for the reaction is
positive, the reaction will occur spontaneously, hence, the cell would generate
electricity. However, if the E0cell for the reaction is negative, the reaction will not take
place, hence, no electric current would flow out of the cell. Note that, if the electrodes
of this cell are interchanged, the cell reaction would be reversed and the E0cell would
change sign.
Electromotive Series (Redox Series)
Element Half Cell Reaction Standard reduction Potential E0 (Volt)
K K+ + e- → K -2.93
Ca Ca2+ + 2e- → Ca -2.87
Na Na+ + e- → Na -2.71
Mg Mg2+ + 2e- → Mg -2.37
Al Al3+ + 3e- → Al -1.67
Zn Zn2+ + 2e- → Zn -0.76
Fe Fe2+ + 2e- → Fe -0.44
Sn Sn2+ + 2e- → Sn -0.14
Pb Pb2+ + 2e- → Pb -0.13
(H) 2H+ + 2e- → H2 0.00
Cu Cu2+ + 2e- → Cu +0.34
Ag Ag+ + e- → Ag +0.80
Au Au3+ + 3e- → Au +1.50
I I2 + 2e- → 2I- +0.54
Br Br2 + 2e- → 2Br- +1.09
Cl Cl2 + 2e- → 2Cl- +1.37
Examples: Calculate the standard cell potential of each of the following cells and
comment on the cell reaction:
(i) Zn(s) / Zn2+(aq) // Cu2+(aq) / Cu(s)

Solution
The half reactions and their electrode potentials are:
Anode reaction (oxidation): Zn(s)→ Zn2+(aq) + 2e- E0 = +0.76

Cathode reaction (reduction): Cu2+(aq) + 2e-→ Cu(s) E0 = +0.34

Net Reaction: Zn(s) + Cu2+(aq)→ Zn2+(aq) + Cu(s)

E0cell = (+0.76) + (+0.34)
E0cell = +1.10 volts
The E0cell for the reaction is positive, hence, the reaction is spontaneous.
(ii) (Pt),H2(g)/ 2H+(aq) // Cu2+(aq) / Cu(s)

Solution
The half reactions and their electrode potentials are:
Anode reaction (oxidation): H2(g)→2H+(aq) + 2e- E0 = 0.00

Cathode reaction (reduction): Cu2+(aq) + 2e-→ Cu(s) E0 = +0.34

Net Reaction: H2(g)+ Cu2+(aq)→2H+(aq) + Cu(s)

E0cell = (0.00) + (+0.34)
= +0.34 volt
The E0cell for the reaction is positive, hence, the reaction is spontaneous.
(iii) Mg(s) / Mg2+(aq) // Ca2+(aq) / Ca(s)

Solution
The half reactions and their electrode potentials are:
Anode reaction (oxidation): Mg(s)→Mg2+(aq) + 2e- E0 = +2.37

Cathode reaction (reduction): Ca2+(aq) + 2e-→Ca(s) E0 = -2.87

Net Reaction: Mg(s) + Ca2+(aq)→Mg2+(aq) + Ca(s)

E0cell = (+2.37) + (-2.87)
= +2.37-2.87 volts
= -0.5 volt
Since E0cell is negative, this reaction will not take place.
(iv) Zn(s) / Zn2+(aq) // Ag+(aq) / Ag(s)

Solution
The half reactions and their electrode potentials are:
Anode reaction (oxidation): Zn(s)→Zn2+(aq) + 2e- E0 = +0.76

Cathode reaction (reduction): 2Ag+(aq) + 2e-→2Ag(s) E0 = +0.80

Net Reaction: Zn(s) + 2Ag+(aq)→Zn2+(aq) + 2Ag(s)

E0cell = (+0.76) + (+0.80)
= +0.76 + 0.80 volts
= +1.56 volts
This reaction will occur spontaneously since E0cell is positive.
(b) A new battery under test for commercial purpose is the zinc-chlorine battery. Its
standard emf, E0cell, is 2.135V. Given that the standard reduction of Zn is -0.763V,
calculate the standard reduction of chlorine.
Solution
Note: the standard reduction potential of Zn is -0.763V, hence, the standard
oxidation potential of zinc is +0.763V
The net reaction of this cell is: Zn(s) + Cl2(g) → ZnCl2(aq)
Hence, the half equations are
Oxidation: Zn(s) → Zn2+(aq) + 2e- E0 = +0.763 V
Reduction: Cl2(g) + 2e- → 2Cl- (aq) E0 = y V
Net equation: Zn(s) + Cl2(g) → Zn2+(aq) + 2Cl-(aq) E0 = 2.135 V

But E0Zn/Zn2+ + E0Cl2/2Cl- = E0cell

0.763 + E0Cl2/2Cl- = 2.135
E0Cl2/2Cl- = 2.135 – 0.763
‫؞‬ E0Cl2/2Cl- = +1.372 V
SOME APPLICATIONS OF ELECROCHEMISTRY IN THE MEDICAL PROFESSION
(1) Electrochemical Biosensors: Used for glucose monitoring in diabetic patients.
(2) Electroconvulsive Therapy (ECT): Uses electric currents to treat severe depression
and other mental health conditions.
(3) Electrochemical Detection of DNA: Used in genetic testing and research.
(4) Electrosurgical Instruments: Use electric currents to cut and coagulate tissue
during surgery.
(5) Pacemakers and Defibrillators: Use electrochemical batteries to deliver controlled
electrical impulses to the heart, correcting irregular heartbeats.
(6) Electrochemical Analysis of Neurotransmitters: For studying brain function and
disorders.
(7) Electrochemical Wound Healing: Uses electrical currents to promote wound
healing.
(8) Electrocardiography (ECG): Used to measure the electrical activity of the heart for
diagnosing heart conditions.
(9) Transcutaneous Electrical Nerve Stimulation (TENS): Uses electrical currents to
relieve pain
(10) Electrolyte Monitoring: Critical for managing patient hydration and electrolyte
balance, especially in intensive care.
 PRACTISE QUESTIONS
(1)(a) Briefly explain electrochemistry (b) In a tabular form, give two differences
between voltaic and Daniel cells
(2) Symbolic depiction of an electrochemical cell is represented as: p / q // r / s. (a)
Identify (i) p (ii) q (iii) r (iv) s (v) / (vi) // (vii) Left side of // (viii) Right side of //
(b) Briefly explain e.m.f of a cell
(3)(a) In a tabular form, state four differences between electrochemical and
electrolytic cells.
(b)(i) Do you think electrochemistry is relevant to your profession?
(ii) Give six reasons for your answer in (bi) above.
(4) Write the net equation for each of the following:
(a) Na+(aq) / Na(s) // Sn(s) / Sn2+(aq)
(b) pt/H+(aq) / H2(g) // Pb(aq) / Pb2+(aq)
(c) Al / Cu2+(aq) // Al 3+(aq) / Cu(s)
(d) H+(aq) / H2(g) // Fe3+(aq) / Fe2+(aq)
(e) Zn2+(aq) / Zn(s) // K(s) / K+(aq)
(f) Mg(aq) / Mg2+(aq) // Al3+(aq) / Al(aq)
(5) (a) Calculate the standard cell potential and comment on the cell reaction of each of
the following (using the table in slide 10):
(i) 2K(s) / 2K+(aq) // Zn2+(aq) / Zn(s)
(ii) Au(s) / Au3+(aq) // Al3+(aq) /Al(s)
(iii) Ca(s) / Ca2+(aq) // 2Ag+(aq) / 2Ag(s)
(iv) Sn(s) / Sn2+(aq) // 2Na+(aq) / 2Na(s)
(v) 2Ag(s) / 2Ag2+(aq) // 2Cl- (aq) / Cl2(g)
(b) Mention the anode and cathode in each of 5(a) above.
(6)(a) An aluminium- iodine battery is currently being tested for commercial use, and
its standard electromotive force (emf), E0cell is 2.231 V. Given that the standard
reduction potential of iodine (I2 /2I-) is +0.542 V, determine the standard reduction
potential of aluminium.
(b) A magnesium-bromine battery is currently being examined for an application. The
standard cell potential (E0cell) for this battery is 3.457 V. Considering the standard
reduction potential of Mg as -2.369 V, determine the standard reduction potential of
bromine.
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