Experiment 2: Concentration Cell (Nernst Equation)

Objectives:

a) To study factors affecting cell potentials.

b) To estimate the concentration of ions in solution using Nernst Equation.

Introduction:

A concentration cell is an electrochemical cell in which both half – cells are the same type but
with different electrolyte concentrations. In concentration cells, the half – cell with the lower electrolyte
concentration act as anode and the one with higher electrolyte concentration is cathode. At anode half
– cell, oxidation occurs to increase the electrolyte concentration and at cathode half – cell, a reduction
reaction occurs to decrease its electrolyte concentration. This oxidation – reduction reaction will
continue until the electrolyte concentrations in both half – cells become equal.

In this experiment, we will measure the voltage of a few voltaic cells such as zinc, magnesium,
iron and copper. A typical voltaic cell consists of two half cells linked by a wire and a salt bridge. Each
half-cell consists of a metal electrode in contact with solution containing a salt of that metal. One is
anode where oxidation takes place and another one is cathode where reduction takes place. Electrons
flow from anode to cathode via wire and the salt bridge allows the migration of ions to prevent the
imbalance charge from building up as electrons leave from anode to the cathode. Using a voltmeter, it
will permit a measurement of voltage or potential difference between half-cell.

Theoretical predictions of tendency to gain electrons are used to predict the voltage difference
between two electrodes. The violated difference between electrodes, the cell voltage, is also called the
electromotive force or emf (Ecell). These theoretically predicted voltages are known as standard emf
(Ecell) under standard conditions of 25˚C, 1 M solution concentration and 1 atm gas pressure. The
quantitative relationship between electrolyte concentration and cell potential is given by the following
Nernst Equation:

𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑒𝑙𝑙 − (ln 𝑄)
𝑛𝐹

(0.0591 V)
= E˚cell - log Q
n
 Ecell is cell potential under non-standard conditions, while E˚cell is cell potential under standard
conditions (calculated from standard reduction potentials), R = 8.314 J/ (mol.K), F = 96,500 C/mol, is the
Faraday’s constant; Q is the reaction quotient, such that, for the reaction:

[𝑍𝑛2+]
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s), 𝑄= [𝐶𝑢2+]

The cell potential calculated from Nernst equation is the maximum potential at the instant the
cell circuit is connected. As the cell discharges and current flows, the electrolyte concentrations will
change, Q increases and Ecell deceases. The cell reaction will occur spontaneously until it reaches
equilibrium, at which point Q = K (the equilibrium constant).

Methods:

A. Effect of Concentration Changes on Cell Potential

1. Effect on Concentration Changes on Cell Potential
a. Galvanic cell is set up using 1 M CuSO4 and 0.001 M CuSO4 solutions.
b. A polished copper electrode is immersed in each solution.
c. A salt bridge is prepared to connect the two redox couples.
d. The cell potential is measured, the anode and cathode is determined.

2. Effect of Complex Formation

a. 5 mL of 6 M NH3 is added to the 1 M CuSO4 solution until any precipitate dissolves.
b. Copper ion forms a complex with ammonia : Cu2+ (aq) + 4NH3 → [Cu(NH3)4]2+ (aq)]
c. Any changes in half – cell and cell potential are observed and recorded.

3. Effect of Precipitate Formation

a. 5 mL of 0.2 M Na2S is added to the 0.001 M CuSO4 solution, that containing the added
NH3.
b. Any changes in half – cell and cell potential are observed and recorded.
B. The Nernst Equation and an Unknown Concentration

1. The diluted solution of Cu (NO3)2 is prepared from 1.0 M of Cu (NO3)2 using 1 mL pipet and 100
mL volumetric flasks.
2. Deionized water is used for dilution ‘to the mark’ in the volumetric flasks.
3. The molar concentration of each solution is calculated.
4. The Zn2+/Zn redox couple used as a reference for this experiment.
5. The cell potential is measured and theoretical cell potential is calculated for solution 4.
6. The steps are repeated with solutions 3 and 2 respectively.
7. A freshly salt bridge is prepared for each cell required.
8. The graph of Ecell (measured) and Ecell (calculated) versus log [Cu2+] is plotted.
9. The concentration of unknown solution is determined using the graph.

Data & Results:

A. Effect of Concentration Changes on Cell Potential

1. Cell potential of ‘concentration cell’ 70.7 mV

Anode reaction Cu(s) → Cu2+(aq) + 2e-
Cathode reaction Cu2+(aq) + 2e- → Cu(s)

2. Cell potential from complex formation 0.425 V

The color change from colorless to dark blue
Observation of solution in half – cell
solution.

3. Cell potential from precipitate formation 0.459 V

Observation of solution in half – cell The color change into light brown color.
B. The Nernst Equation and an Unknown Concentration

Concentration
Solution
of Cu(NO3)2 Ecell (measured) (v) Ecell (calculated) (v)
number
(mol/L)
1 0.1 -1 0.935 1.13
2 0.01 -2 0.915 1.1596
3 0.001 -3 0.895 1.1892
4 0.0001 -4 0.880 1.2188
5 Unknown Graph 0.889 1.1541

Ecell for the solution of unknown concentration: 0.889

Molar concentration of Cu2+ in the unknown: 0.0388 M

Calculations:

Concentration of Concentration of Cu(NO3)2

Cu(NO3)2 (0.0591 V)
= Eocell - log Q
(mol/L) n
0.1 =1.13 – 0 = 1.13
0.01 =1.13 – (-0.0296) = 1.1596
0.001 =1.13 – (-0.0592) = 1.1892
0.0001 =1.13 – (-0.0888) = 1.2188
0.0388 =1.13 – (-0.0241) = 1.1541
 Ecell (measured) vs Log [Cu2+]
0.94
0.93
0.92
0.91
0.9
0.89 Ecell (measured) (v)

0.88
0.87
0.86
0.85
-1 -2 -3 -4

Ecell (calculated) vs Log [Cu2+]

1.24

1.22

1.2

1.18

1.16
Ecell (calculated) (v)
1.14

1.12

1.1

1.08
-1 -2 -3 -4
Discussion:

In this experiment, voltmeters are used to measure the reading of cell potential of 1 M CuSO4
and 0.001 M CuSO4 solutions. The voltage of a reaction containing a metal strip of copper in separate
aqueous solutions with a salt bridge in between to balance charge as reaction progressed. The voltage
reading is 70.7 mV and it’s recorded to measure the capacity of the movement electron from anode to
cathode. Then, 5 mL of 6 M NH3 is added to the 1 M CuSO4 solution until any precipitate dissolves. The
color changes from colorless to dark blue solution. The cell potential is increases to 0.425v. Adding
ammonia solution causes the complex [Cu(NH3)4]2+ to form in the cathode half-cell (0.001M solution). As
the concentration of Cu2+ ions in the half-cell decreases, the overal cell potential will increase. This is
due to the increasingly widening gap between concentrations of the two half cell solutions. For the last
step, 5 mL of 0.2 M Na2S is added to the 0.001 M CuSO4 solution, that containing the added NH3. The
color then change to light brown solution. The cell potential also increases to 0.459v. Adding Na2S will
causes formation of a complex ion with copper solution. Thus will increases the cell potential.

From the plotted graph of Ecell (measured) versus log [Cu2+], we can determined the molar
concentration of unknown which is 0.0388 M. Based on the Ecell calculated for copper, the value are
higher than the measured value. It became apparent during the experiment that enormous error
occurred in the portion regarding temperature and change in cell potential. It appears that the
functionality of the voltmeter was not correct, therefore giving results that were not accurate. Anything
at all which causes any internal resistance in the cell or the circuit being used to measure it will reduce
the measured potential. As well, frequently, non – standard conditions may be used in a lab. The
standard cells are for 1 M solutions. They are measured at 25 degrees Celsius. Differences in these
conditions will cause changes. If a reactant or product is a gas, it needs to be bubbled over an electrode
with a pressure of 1 atm.

Conclusion:

We are able to study factors affecting cell potentials and also able to estimate the concentration
of ions in solution using Nernst Equation.
Questions:

A. Effect of Concentration Changes on Cell Potential

1. Explain why a potential is recorded.
A difference in concentration of Copper (II) Sulphate solution causes a difference in
potential between the two solutions. This therefore causes one half cell to undergo
oxidation while the other goes reduction.

2. Explain why the potential changes with the addition of NH3 (aq).
A dark-blue precipitate is formed at 0.001 M CuSO4 solution half-cell. Adding ammonia
solution causes the complex [Cu(NH3)4]2+ to form in the cathode half-cell (0.001M solution).
This therefore changes the potential of the cell. As the concentration of Cu2+ ions in the half-
cell decreases, the overal cell potential will increase. This is due to the increasingly widening
gap between concentrations of the two half cell solutions.

3. Explain why the potential changes with the addition of Na2S.

The potential increases when Na2S is added. This is because the reaction between NH 3 and
Na2S to produce insoluble (NH4)2S, formation of a complex ion with copper solution. Thus
will increases the cell potential.

4. How would the cell potential have been affected if the NH 3 (aq) and/or the Na2S (aq) had
been added to the 1 M CuSO4 solution instead of the 0.001 M CuSO4 solution of the cell?
Explain.
When 1 M CuSO4 is added instead of 0.001 M CuSO4 , the cell potential will decrease. This is
because a higher concentration of CuSO4 will act as a reducing agent. This will result in a
further addition of reducing agent which will decrease the chances of redox compared with
the lower concentration of CuSO4.
B. The Nernst Equation and an Unknown Concentration

1. How would you adjust the concentrations of Cu2+ and Zn2+ for the Cu – Zn cell to maximize
the cell potential? Explain.
Any change to each ion to the system that pushes it further away from equilibrium, causes
the potential to go up. Any change to the system that pushes the system towards
equilibrium, causes the potential to go down. Therefore any changes that are made to both
Zn2+ and Cu2+, the system either moves closer or away from the equilibrium. The reaction
quotient for example Q= [Zn2+]/ [Cu2+] of equation Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s) of
this redox reaction helps to understand the concept. For example when all concentrations
are 1 M the Q will equal 1. But this reaction is spontaneous which K > 1. As the cell reaction
proceeds and Q approaches K the cell potential drops. Therefore when both the
concentrations of Zn2+ and Cu2+ are changed Q= [Zn2+]/ [Cu2+]) will be effected on their ratio,
which will effect on the cell potential also. For example the potential of the cell increases
when the concentration of Cu2+ increases Zn2+ is constant at 1.0 M.

References:

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help/questions-and-answers/5-adding-ammonia-solution-containing-copper-ions-reduces-
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measured-cell-potential-different-from-the-theoretical-potential
3. Cell Potential from Precipitate. Retrieved October 6, 2017 from
https://www.coursehero.com/file/pnsu7h/3-Cell-potential-from-precipitate-formation-105-V-
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5. Spontaneous Reaction. Retrieved October 6, 2017 from
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