KWAME NKRUMAH UNIVERSITY OF SCIENCE AND

TECHNOLOGY, KUMASI

DEPARTMENT OF CHEMISTRY
YEAR TWO (CHEM 269)

PRACTICAL CHEMISTRY III

TITLE: ELECTROCHEMISTRY

NAME: OPOKU ERNEST

EMAIL: ernopoku@gmail.com

DATE: 29TH SEPTEMBER, 2013

 TITLE: ELECTROCHEMISTRY

AIMS AND OBJECTIVES:

1. To compare the measured and calculated values of the EMF of the Cu2+/Cu half cell
at different concentration of Cu2+.
2. To find the end –point of the sodium chloride-silver nitrate titration by EMF
measurements.
3. To determine the equilibrium constant of a reaction, from measurement of the EMF of
a cell when the- reaction is not at equilibrium.

INTRODUCTION
Electrochemistry is concerned with the interrelation of electrical and chemical effects.
Reactions involving the reactant – the electron. Chemical changes caused by the passage of
current. An electrochemical system is not homogeneous but is heterogeneous.
Electroanalytical chemistry encompasses a group of quantitative analytical methods that
are based upon the electrical properties of an analyte solution when it is made part of an
electrochemical cell. These methods make possible the determination of a particular
oxidation state of an element.
-
Ox + ne ↔ Red
There are two general types of electrochemical methods: potentiometric (no current,
equilibrium potential) and voltammetric (current measured as a function of the applied
potential.
Electrochemical cells consist of two electrodes: an anode (the electrode at which the
oxidation reaction occurs) and a cathode (the electrode at which the reduction reaction
occurs).
+2 +2 +2 -
Cu(s) + Zn ↔ Cu + Zn(s) Cu(s) ↔ Cu + 2e

+2 -
(oxidation) Zn + 2e ↔ Zn(s) (reduction)

There are two types of electrochemical cells: galvanic (ones that spontaneously produce
electrical energy) and electrolytic (ones that consume electrical energy).

o 2.303 RT
E= E ´+ [Ox]
nF [Red]
log
The potential that develops in a cell is a measure of the tendency for a reaction to proceed
toward equilibrium.We use concentrations in the Nernst equation, but really activities
are the proper term. The activity of a specie can be defined as the ability of a
species to participate an equilibrium reaction involving itself.
+3 - +2 +2
Example: Fe + e ↔ Fe FeCl , etc. depends on ionic strength

Ecell = Ecathode – Eanode

 ∆Grxn = - nFEcell
∆Grxn = -RTlnKeq Key equations

All cell potential measurements require two electrodes!

1. AgCl(s) + e- ↔ Ag(s) + Cl-
E = Eo + (0.059/n)log1/[Cl-]
2. Hg2Cl2(s) + 2e- ↔ 2Cl- + 2Hg(l)

E = Eo + (0.059/2)log1/[Cl-]2

n = number of electrons transferred per mole, 2.303 RT/F = 0.059 V

Cu+2 + H2(g) ↔ Cu(s) + 2H+

Zn/ZnSO4 (aZn+2 = 1.00)//CuSO4 (aCu+2 = 1.00)/Cu

Anode (oxidation) Cathode (reduction)

Electrode reaction kinetics are affected by the electrode surface cleanliness, surface
microstructure, and surface chemistry.

CHEMICALS AND EQUIPMENT

1. 1M CuSO4, 0.1M CuSO4, 0.01M CuSO4 and 0.001M CuSO4 solutions
2. 1M ammonia solution
3. 1M KCl
4. Calomel electrode
5. Distilled water
6. 200mL measuring cylinder
7. 1mL pipette
8. 4 beakers
9. Banana clip
10. Copper electrode
11. Filter paper
12. Volt meter
13. 8M nitric acid

PROCEDURE

A. The effect of concentration on EMF

1. Enough amounts of 1M CuSO4, 0.1M CuSO4, 0.01M CuSO4, and 0.001M CuSO4
solution were prepared and poured in clean dry different beakers.
2. The calomel electrode was connected to the middle socket of the multimeter. The
rubber cap was removed from the tip of the electrode.
 3. A crocodile clip lead was connected into the bottom socket of the meter. A clean
piece of copper was placed into a crocodile clip to form a copper electrode.
4. The copper electrode was cleaned by immersion of the copper in 8M AgNO3
provided in a fumed hood followed by rinsing with water.
5. A copper electrode was dipped into the beaker containing 0.001M sulphate solution
and the EMF recorded with the help of the voltmeter at 200mV range.
6. The electrode and the beaker were rinsed with distilled water and the calomel
electrode dipped into a solution of 8M nitric acid.
7. The procedure was repeated for the other concentrations of the sulphate solution and
the results tabulated.

TABLE OF RESULTS

Concentration of CuSO4 Measured Ecell

( mol/L) (mV)
0.001 73.93
0.01 100.90
0.1 104.97
1.0 119.73

CALCULATION
electrode potential of the saturated calomel electrode = 0.274V at 18oC
The reaction that occurred is as shown below
Cu2+ + 2e- Cu LHE
Cu Cu2+ + 2e- RHE
Cu2+ + Cu Cu + Cu2+ cell reaction
From the equation
E(Cu2+/Cu)= 0.247-E(cell)

E(Cu2+/Cu) (0.001M) = 0.247- 73.93×10-3

=0.17307V

E(Cu2+/Cu) (0.01M) = 0.247- 100.90×10-3

=0.14610V

E(Cu2+/Cu) (0.1M) = 0.247- 104.97×10-3

=0.14203V
E(Cu2+/Cu) (1.0M) = 0.247- 119.73×10-3
=0.12727V

Concentration of CuSO4 E(cell)/mV E(Cu2+/Cu)/V E(Cu/Cu2+)/V

( mol/L)
0.001 73.93 0.17307 -0.17307
0.01 100.90 0.14610 -0.14610
 0.1 104.97 0.14203 -0.14203
1.0 119.73 0.12727 -0.12727

From
E= Eo -0.059 log [reduced form]
n [oxidized form]
where n= number of electrons in one half-cell= 2
Eo= the standard electrode potential of the copper electrode = 0.337V
[reduced form]= 1M

Concentration of CuSO4 [reduction form] 0.059Log [reduction form] E/V

(mol/L) [oxidation form] [oxidation form]

1.000 1 0.0000 0.3370

0.100 10 0.059 0.2780
0.010 100 0.118 0.2190
0.001 1000 0.177 0.1600

B. Determination of an Equilibrium constant

1. 50mL of 1M ammonia solution and 2mL of 0.01M copper sulphate solution was
measured into a beaker and swirled. A reasonable amount was afterwards poured into
a beaker.
2. A reasonable amount of 0.1M of copper sulphate was put into another cleaned
beaker.
3. Two copper electrodes were dipped into the two solutions.
4. A filter paper was soaked with 1M KCl and used as salt bridge.
5. The EMF of the two half-cells was taken at 2.5V range and the result recorded.

The recorded EMF was 0.394V at 250mV range, hence the voltage was 250mV

Cu/Cu2+/ (salt bridge) Cu (NH3)42+/Cu.

From
E(cell)= Eo(cell) – 0.059 log [Cu2+][NH3]4
2 [Cu(NH3)42+]
Eo(cell)=E(cell) + 0.059 log [Cu2+][NH3]4
2 [Cu(NH3)42+]
Eo(cell)= 0.025+ 0.0295 log (0.1)(0.96)4 = 0.0625V=62.5 mV
3.85×10-4
o
log K = 2E (cell)/0.059 = 2×0.0625/0.059 = 2.1186
K = log-1 2.1186 = 131.401

DISCUSSION
By carefully examining the EMF values obtained, it was observed that as the concentration of
the copper sulphate solution increases the EMF values of the cells also increases. This
observation is due to the fact that there are more ions in solutions of higher concentrations
than solutions of lower concentration which consequently led to the attainment of such
results. The results calculated for E (Cu/Cu2+) are negative because every reduction half-cell
reaction has a corresponding standard reduction potential Eored. If the reaction is reversed, it
becomes an oxidation half-cell with a corresponding standard oxidation potential, Eoox. For
any given half-cell reaction, Eoox = -Eored. When the equilibrium constant K>>>1, the
equilibrium position of the reaction lies to the right and favors the products and vice versa.
Thus the equilibrium constant of this experiment showed that the reaction favors the
production of the Cu2+ ions in solution since the calculated value for K>>>1.

PRECAUTIONS
1. A crucial care was taken to avoid the electrode getting into contact with the solution in
order to obtain accurate values of the EMF.
2. The salt bridge was well immersed into both of the Cu (NH3)42+ solution and the CuSO4
solutions.
3. The copper electrode was immersed in 8M nitric acid followed by rinsing after each
use.
4. Reading of values from the pipette were taken from the eye level to avoid parallax
errors.

CONCLUSION
From close observation of the values obtained from the experiment and making reference
from the understated references, EMF of a cell increases as the concentration of the solution
increases. Also the equilibrium constant of the reaction can be determined from its EMF
values.

REFERENCES
1. General Chemistry, Raymond Chang, 5th edition, pages 630-640.
2. Chemical Technician Ready Reference Handbook 2nd edition by Shugar and
Bauman pages 592- 593.
3. Health Chemistry Laboratory Experiment 2nd edition by Micheal .A. Dispezio
page 310-312.
4. Textbook of Practical Chemistry 4th edition (2001) by Wesley. D. Smith pages 620-633.
5. Practical Chemistry 4th edition (1990) by Francis Kinkier pages 745-748.