LABORATORY REPORT

CHM 578

EXPERIMENT 1 : GALVANIC CELL

Name : Aisyah binti Ahmad Fauzi

Matrix Id : 2019328925
Group : AS2223A1
Lecturer’s Name : Dr Normonica Binti Ahmad
Experiment 1 : Galvanic Cell

Objectives :

a) To measure the relative reduction potentials for a number of half cell (redox) couples
in a galvanic cell
b) To develop an understanding of the movement of electrons, anions and cations in a
galvanic cell
c) To study factors affecting cell potentials
d) To estimate the concentration of ions in solution using the Nernst Equation

Introduction

If a metal electrode is immersed in an aqueous solution containing a metal cation, an

equilibrium is established which leads to negative charge formation on the electrode. This
configuration of electrode and solution is called half-cell. Two half-cells can be combined to
form an electrochemical cell. The equilibrium condition in an electrochemical cell is that the
electrochemical potential, rather than the chemical potential, of a species is the same in all
parts of the cell. Electrochemical cell can also be used to provide power, in which case they
called batteries. Electrochemical cells in which the reactants can be supplied continuously are
called fuel cells

In an electrochemical cell (voltaic cell, galvanic cell), reduction and oxidation take place in
such a way that electric voltage is generated between two electrodes. The anode is the
electrode where positive ions are solvated in the electrolyte, forming an anode current, or
negative ions (anions) are coming onto the electrode from the electrolyte. At the other
electrode, the cathode, the current flows in the opposite direction. By adding a counter
potential, it is possible to make the anode and cathode currents of equal magnitude but with
different signs.

No measurable transport of charge takes place if the half cell is not connected to another half
cell. Otherwise, accumulation of charge would generate a counter field. Very quickly, a
voltage is created between the metal rods. If the metal rods are connected, a current will flow
between the two electrodes. The voltage can be measured with the help of a voltmeter.
Procedure :

A. Galvanic Cell – Reduction Potentials of Several Redox Couples

1. Four small beakers was obtained and filled with 0.1M solutions of Zn(NO₃)₂ ,
Cu(NO₃)₂ , FeSO₄ and MgSO₄ respectively. Copper, zinc, and iron metal strips has
been polished with sand paper and rinsed briefly with deionized water
2. Cu strip has been placed in the Cu(NO₃)₂ solution and Zn strip in the Zn(NO₃)₂
solution. A piece of filter paper is rolled and flattened and has been soaked in 0.1M
KNO₃ solution. The filter paper, that acts as the salt bridge, is then folded and the end
was inserted into two beakers. One electrode is connected to the negative terminal and
the other to the positive terminal
3. The positive cell potential has been recorded. The metal strips that serves as cathode
and anode is identified. Half-reaction at each electrode is written . the two half-
reaction to write the equation for the cell reaction is combined
4. The cell potential for all possible galvanic cells that can be constructed from the other
redox couples has been determined. A new salt bridge for each galvanic cell has been
prepared
5. The reduction potentials of all other redox couples has been determined

B. Effect of Concentration Changes on Cell Potential

1. The galvanic cell has been set up using 1M CuSO₄ and 0.001M CuSO₄ solutions. A
polished copper electrode has been immersed in each solution. To connect the two
redox couples, a salt bridge is prepared and inserted the end to each two beakers.
2. The cell potential has been measured and the cathode and anode has been
determined. Equation for the reaction occurring at each electrode has been written
3. 5ml of 6M NH₃ is added to 0.001M CuSO₄ solution, until any precipitate redissolves.
Any changes in the half-cell and the cell potential has been observed
C. The Nernst Equation and an Unknown Concentration
1. Solutions 1 through 4 has been prepared using a 1ml pipet and 100ml volumetric
flasks. 0.1M of Cu(NO₃)₂ is used in this experiment. 1ml of Cu(NO₃)₂ is added to
solution 2. Deionized water is used for dilution to the volumetric flask mark. The
molar concentration of each solution is calculated
2. Repeat step 1 to solution 3 and 4 respectively
3. Zn redox couples is the reference half-cell for this part of the experiment. Two half-
cells with a new salt bridge is connected. The electrodes is connected and the
potential difference has been recorded.
4. The theoretical cell potential has been calculated using the table of standard reduction
potentials and the Nernst equation.
5. Step 3 has been repeated with solution 2, 3 and 4 respectively. A freshly prepared salt
bridge has been used for each cell
6. Ecell(measured) and Ecell(calculated) versus log [Cu²⁺] has been plotted on a graph
paper for the four concentrations of Cu(NO₃)₂
7. Cu(NO₃)₂ with an unknown copper ion concentration has been obtained and set up a
galvanic cell. Cell potential has been determined. The unknown copper ion
concentration in the solution has been determined using the graph
Data and Result

A. Galvanic cell – Reduction Potentials of Several Half Cell Couples

Galvanic Measure Anod Equation for anode Cathod Equation for cathode
cell d Ecell e reaction e reaction

Cu – Zn 0.30 V Zn Zn → Zn²⁺ + 2e⁻ Cu Cu²⁺ + 2e⁻ → Cu

Cu – Fe 0.15 V Fe Fe → Fe²⁺ + 2e⁻ Cu Cu²⁺ + 2e⁻ → Cu
Mg – Cu 0.40 V Mg Mg → Mg²⁺ + 2e⁻ Cu Cu²⁺ + 2e⁻ → Cu
Mg – Fe 0.20 V Mg Mg → Mg²⁺ + 2e⁻ Fe Fe²⁺ + 2e⁻ → Fe
Table 1 : Observations an interpretations from the galvanic cells

Overall equations for three cell reactions :

Cu – Zn

Zn + Cu²⁺ → Zn²⁺ + Cu

Cu – Fe

Fe + Cu²⁺→ Fe²⁺ + Cu

Mg – Fe

Mg + Fe²⁺→ Mg²⁺ + Fe

Mg – Cu

Mg + Cu²⁺→ Mg²⁺ + Cu

Redox Couples Reduction potential Reduction potential % Error

(measured) (Calculated)
Cu – Zn 0.30 V 0.42 V 28.57%
Cu – Fe 0.15 V 0.10 V 5%
Mg – Fe 0.20 V 1.93 V 89.64%
Mg – Cu 0.30 V 2.71 V 88.93%
Table 2 : Percentage error of redox couples

% Error
Cu – Zn

% Error = |(measured – calculated)/ calculated| x 100%

= |(0.30 – 0.42)/ 0.42| x 100%

= 28.57%

Cu – Fe

% Error = |(0.15 – 0.10)/ 0.10| x 100%

= 5%

Mg – Fe

% Error = |(0.20 – 1.93)/ 1.93| x 100%

= 89.64%

Mg – Cu

% Error = |(0.30 – 2.71)/ 2.71| x 100%

= 88.93%

B. Effect of Concentration Changes on Cell Potential

1. Cell potential of ‘concentration cell’ : 0V

Anode reaction : Cu → Cu²⁺ + 2e⁻

Cathode reaction : Cu²⁺ + 2e⁻ → Cu

Explain why a potential is recorded

To observed if there is any movement of electrons between solutions with same

solution but different concentrations

2. Cell potential from complex formation : 0.20V

Observation of solution in half-cell :

Explain why the potential changes with the addition of NH₃?

The potential changes as concentration of the solution decreases. NH₃ is used to

reduced the Cu²⁺ into a complex ion, therefore decreases the ionic Cu concentration
and create potential differences.

3. How would the cell potential have been affected if the NH₃ had been added to the 1M
CuSO₄ solution instead of the 0.001M CuSO₄ solution of the cell? Explain.

The cell potential between the solution is decrease as the concentration of 1M CuSO₄
decrease and cause the different cell potential between them to reach equilibrium
smaller.

C. The Nernst Equation and an Unknown Concentration

 Solutio Concentration of Log [Cu²⁺] Ecell Ecell
n Cu(NO₃)₂ (measured) (calculated)
Number
1 0.1M -1 0.70 0.42
2 0.001M -3 0.50 0.36
3 0.00001M -5 0.20 0.30
4 1 X 10⁻⁷ M -7 0.15 0.24
Table 3 : concentrations of the Cu(NO₃)₂ solutions and the measured and calculated cell
potentials

Overall equation : Zn + Cu²⁺ → Zn²⁺ + Cu

0.1M

Q = [Zn²⁺]/[Cu²⁺]

= 0.1/0.1

=1

Ecell = E⁰cell – RT/nF ln Q

Ecell = 0.42 – (8.314)(298K)/(2)(96500) ln 1

= 0.42 V

0.001M

Q = [Zn²⁺]/[Cu²⁺]

= 0.1/0.001

= 100

Ecell = 0.42 – (8.314)(298K)/(2)(96500) ln 100

Ecell = 0.42 – 0.01284 ln 100

= 0.36 V
0.00001M

Q = [Zn²⁺]/[Cu²⁺]

= 0.1/0.00001

= 10000

Ecell = 0.42 – (8.314)(298K)/(2)(96500) ln 10000

= 0.42 – 0.01284 ln 10000

= 0.30 V

1 X 10⁻⁷ M

Q = [Zn²⁺]/[Cu²⁺]

= 0.1/1 X 10⁻⁷

= 1000000

Ecell = 0.42 – (8.314)(298K)/(2)(96500) ln 1000000

= 0.42 – 0.01284 ln 1000000

= 0.24 V

2. From plot of Ecell versus log [Cu²⁺], account for any significant difference between the
measured and calculated Ecell values?

Based on Ecell measured graph, the value of slope is 0.0917 while the slope in E cell
calculated is (theoretical) 0.03. there is slightly different of 0.0617 between them.

3. Ecell for the solution of unknown concentration : 0.45 V

Molar concentration of Cu²⁺ in the unknown : 0.00016M

 Molar concentration of Cu2+ in unknown (based on graph) : Log [Cu2+] unknown
is -3.8. therefore, 10^(-3.8) = 0.00016M

4. How would you adjust the concentrations of Cu²⁺ and Zn²⁺ for the Cu – Zn cell to
maximize the cell potential? Explain

The concentration Zn(NO₃)₂ needs to be decrease while the concentration of Cu(NO₃)₂

needs to decrease. This will gives a lower value of Q and based on Nernst value the lower the
value of Q will increase the value of Ecell (V).

Discussion

For reduction potentials of several redox couples, few beakers was added with different types
of solution with same concentration which is 0.1M to determine the cell potential for redox
couples Cu-Zn, Cu-Fe, Mg-Fe and Mg-Cu. Different values of Ecell has been observed. This
is because different types of electrodes shows different value of Ecell. Cu-Zn has Ecell value
of 0.30, Cu-Fe has the value of 0.15 and Mg-Fe and Mg-Cu has Ecell value of 0.20 and 0.40
respectively. During attempts of identifying the electrodes of the redox couples, negative
potential voltmeter reading has been obtained. In order to obtain positive potential reading,
the wires connected on the electrodes has been reversed. Salt bridge is used to connect both
electrodes and to determine the reduction potential. Without the salt bridge, the solution in
the anode compartment would become positively charged and the solution in the cathode
compartment would become negatively charged. The salt bridge is wet with K(NO₃)₂ as the
salt bridge needs to maintain the neutrality in the system by providing enough negative ions
equal to the positive ions during oxidation.

To determine the relative reduction potentials of the redox couples, a table of standard
reduction potentials is used to determine the calculated reduction potential. For Cu-Zn, the
calculated reduction potentials is 0.42V. Cu-Fe has the calculated reduction potentials of
0.10V. For Mg-Fe, calculated reduction potential is 1.93 while Mg-Cu is 2.71V. percentage
error has been calculated to determine the difference value between the measured and
calculated reduction potential. For Cu-Zn and Cu-Fe, the percentage error is 28.57% and 5%
respectively. Both redox couples shows small value of error. This indicates that there are
slight difference between measured and calculated reduction potentials. For Mg-Fe and Mg-
Cu,the percentage error is 89.64% and 88.93% . the value of error is bigger which shows that
there is a huge difference value between measured and calculated reduction potentials for
both redox couples.

Some errors might occur during the experiment. Some of the error is theoretical error. The
calculated reduction potentials value has been obtained using controlled environment where
the temperature room is 25⁰C and pressure of 1 atm. For measured reduction potentials,
reading might be obtained in different room temperature that makes slight difference between
the values. Other than that, random error might occur where error in judgment of an observer
when reading the scale of the voltmeter.

For the next experiment, test the electrode potentials create in voltmeter with the same
electrode but differ of electrolyte concentration. As observed, there is no potential difference
between the two half-cells as the electrodes used are the same and the result is 0V. The
0.001M CuSO4 solution undergoes oxidation while 1.0M CuSO4 undergo reduction as
electron moves from low concentration to higher concentration. Then, 5 ml of NH 3 was
added into 0.001M CuSO4. Ammonia solution is colourless liquid, but after added into
0.001M CuSO4, the solution turns light blue as Cu2+ ion will reduced into a complex
ammonia ion which gives colour into blue . The Cu2+ solution is undergoes reduction in
0.001M solution and the reading of the cell potential is 0.20V. In equation, the solution
produces the complex ion of Tetraamminecopper(II) sulphate.

Eq: Cu2+ + 4NH3  [Cu(NH3)4]2+

Next, experiment has been conducted with objectives to Ecell using the Nernst equation and
calculate the concentration of unknown Cu(NO₃)₂ using the graph plot. During this
experiment, Zn(NO3)2 stay the same as the half cell solution. The variables is only the
concentration of the Cu(NO3)2 solution. In making the solution, serial dilution technique from
the stock solution of 0.1M Cu(NO3)2 is used to make solution 2,3 and 4.

As the Zinc has lower standard electrode potential than Copper in table, therefore Zn
always occur oxidation while Cu2+ will undergoes reduction. Reading of Ecell value is 0.70V,
0.50V, 0.20V and 0.15V for solution 1,2,3 and 4 respectively. Based on the graph, we can
conclude that the decreasing of the log [Cu2+] will decrease the Ecell. Then, we can find the
concentration of the unknown from the E cell that has measured from the graph. We found that
the unknown concentration is 0.00016M which is lower concentration than solution 1. Then
to know the theoretical Ecell value we used the Nernst Equation. The value of E cell obtained
was 0.42V, 0.36V, 0.30V and 0.24V for solution 1,2,3 and 4 respectively. From, the Nernst
Equation, Ecell decrease as concentration decrease.

Conclusion

The relative reduction potentials for a number of half-cell couples in a galvanic cell has been
measured. An understanding of the movement of electrons, anions and cations in a galvanic
cell had been developed. Next, factors affecting cell potentials has been studied and the
concentration of ions in solution using the Nernst equation is estimated

References

Engel, T., & Reid, P. (2010). Physical Chemistry. New Jersey: Pearson Education inc.

Larsson, S. (2012). Chemical Physics : Electrons and Excitations. Florida: CRC Press.