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CHEM 102L LAB 9

Electrochemistry: Voltaic and Electrolytic Cells

OBJECTIVES
1. Set up and test the voltage of a various galvanic electrochemical cells.
2. Set up an electrolytic cell and determine what is being oxidized and reduced.
3. Be able to draw and label an electrochemical cell and write the shorthand notation for the cell.
4. Determine the reactivity of different metals used in the experiment.
5. Use the Nearst Equation to calculated the E​cell​ at non-standard conditions.
6. Understand the mathematical relationship between E​o​cell​, ​Δ​Go​​ , and the equilibrium constant, K.

INTRODUCTION

Oxidation ​is when an atom loses electrons.​ Reduction​​ is when an atom gains electrons. A
chemical reaction where one species loses electrons and another species gains electrons is called a
redox reaction​​. In such reactions, the substance that gets oxidized (loses electrons) is called the
reducing agent​​. The substance that gets reduced (gains electrons) is called the ​oxidizing agent​​.
In many redox reactions, there is a complete transfer of electrons from the substance being
oxidized to the substance being reduced. When these electrons travel through a conductor, such as a
wire, electric current can be generated and measured in volts. In this arrangement, there are two
half-reactions​. There is an oxidation half-reaction and a reduction half-reaction. In this lab each
reaction takes place in a different container. These containers are called ​half-cells​. A wire connects the
two half-cells through a device that measures current called a ​voltmeter​. In order to complete the
electrical circuit, ions must be free to travel from one half-cell to another. This is made possible by
connecting the two half-cells with a ​salt bridge​​. A salt bridge is a U-shaped tube or paper, saturated
with a non-reactive salt solution, that connects the two half-cells of a redox reaction and allows ions to
migrate from one cell to another (Figure 1).

Figure 1. A Galvanic (Voltaic) Electrochemical Cell

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The shortened notation for the previous electrochemical cell can be written:

Anode Half-Cell || Cathode Half-Cell


Electrode | Anode Soln || Cathode Soln | Electrode
Zn(​s​) | Zn​2+​ (1 M) || Cu​2+​ (1 M) | Cu(​s​)

In each half-cell a conductor is needed to establish the electric current. These conductors are called
electrodes​​. In the oxidation half-cell, the electrode is called the ​anode​​. The anode is considered to be a
negative electrode because electrons are generated there. In the reduction half-cell, the electrode is
called the ​cathode​​. The cathode is considered to be a positive electrode because electrons are
attracted to it. The current generated by an electrochemical cell is called ​electrochemical potential ​(​Eo​​ ​).
Electrochemical potential is the difNirence in “potential” of the two half-reactions that can generate
current. The difNirence is a comparative measurement (compared to a standard hydrogen half-cell) and
is measured in volts (Table 1). At standard conditions (25​o​C, 1atm, 1M), the electrochemical potential
can be calculated from a Table of Standard Reduction Potentials as follows:

E​°​cell​ = ​E°​ ​ox​ + ​E​°​red

The ​Nearst Equation ​is used to calculate the cell potential when data is collected at conditions that are
not at standard conditions.

The dependence of a cell’s voltage is related to the concentrations of its reactants and products.
The​ Nernst Equation ​represents this relationship:

​E = E​o​​ ​ – ​RT​​ ln ​Q ​ here ​E​ is the potential of the cell.


w
​nF E​ o​​ ​ is the potential of the cell at standard conditions
R ​ ​ is the gas constant 8.314 J/mol-K
T​​ is the temperature in Kelvin
​n​ are the moles of electrons transNirred
​F​ is Faraday’s constant (96500 Coulombs/mole)
and ​Q​ is the reaction quotient (products/reactants)

From the above formula at 25​o​C, a shorted form of the Nearnst Equation can be written as follows.

E​cell​ = E˚​ ​cell​ - ​0.05916​ log​ [​ products]p​


n [reactants]r​

There is a relationship between the E​o​cell​, ​Δ​Go​​ , and the equilibrium constant, K. These relationships are
summarized by the following equations:

E˚​cell​ = (0.05916​/​n) log K

∆G˚ = –nFE˚​cell

K = 10 (n​ *E˚cell) /0.05916)

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In this experiment you will create an electrochemical cell, and observe a redox reaction,
measure electrochemical potential of a redox reaction and compare it to the accepted value for that
redox reaction. You will also use the Nernst equation to determine the cell potential of different
reaction concentrations and compare them to the experimental values. Finally, the above equations will
be used to understand the relationship between E​o​cell​, ​Δ​Go​​ , and the equilibrium constant, K.

In the second part of this lab, you will create an ​electrolytic cell.​​ This is a device that uses
electric current to drive a non-spontaneous reaction. You will be using a 9-volt battery to cause the
electrolysis of a sodium iodide solution and figure out which species are being oxidized and reduced
using your observations and the ​Standard Reduction Potential Table provided.

Figure 2. An Electrolytic Electrochemical Cell

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MATERIALS
black and red coated wire with alligator clips
safety glasses DC voltmeter phenolphthalein
copper strip, nickel strip zinc strip, aluminum strip pipet
sand paper plastic cups 9-Volt battery with terminal
0.50 M KNO​3​, 0.10 M ZnSO​4​, 0.10M NiSO​4​, 0.10 M Al(NO​3​)​2,​ 0.0020 M ZnSO​4, and
​ 0.10 M CuSO​4
NaI​ (saturated
​ solution)

PROCEDURE - Part A – Constructing a Voltaic Cell.


1. Using a sanding block, clean the strips of copper, zinc, nickel, and aluminum.
2. Using a black marker, label five plastic cups: 0.10 M CuSO​4​, 0.10 M ZnSO​4​, 0.10M Al(NO​3​)​3​, 0.10 M
NiSO​4​, and 0.0020 M ZnSO​4​.
3. Place a strip of metal in its own solutions. Example Zn metal in a solution of Zn​2+​.
4. Place a salt bridge (strip of filter paper soaked in 0.50 M KCl) so it is immersed in the solutions in
each cup.
5. Place a clean piece of Zn metal in the Zn​2+​ solution. Do not place the Zn strip in the other
solutions – it will react! Secure the Zn strip to the plastic cup using the ​red​​ alligator clip.
6. Place a clean piece of Cu metal in the Cu​2+​ (0.10M) solution. Secure the Cu strip to the plastic cup
using the ​black​​ alligator clip.
7. Attach the other end of the red and black wires to the same colored leads on the voltmeter. Turn
the voltmeter to read 2000 mV (DC) - then turn on the voltmeter. Record the voltage you read
from the voltmeter. Simply divide the mV value by 1000 to obtain V.
8. Use a strip of filter paper soaked in 0.5M KNO​3​ as a salt bridge. Place the plastic cups next to each
other with the salt bridge in each solution. Now read the voltmeter again and record the voltage.
9. Repeat steps 5-7 to obtain voltages for the remaining solutions with the Cu​2+​ (0.10 M) half-cell.
If the voltage is positive, the metal half-cell is oxidized and the copper half-cell is reduced. If the
voltage is negative, the metal half cell is reduced and the copper half cell is oxidized.

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DATA – VOLTAIC CELLS

​ ​(0.10M) // Cu​+2​
1. Zn / Zn​+2​ ​ ​(0.10M) / Cu ​without​ the salt bridge ____________ V

​ ​(0.10M) // Cu​+2​
2. Zn /Zn​+2​ ​ ​(0.10M) / Cu ​with the salt bridge ____________ V

​ ​(0.10M) // Cu​+2​
3. Al / Al​+3​ ​ ​(0.10M) / Cu ​with the salt bridge ____________ V

​ ​(0.10M) // Cu​+2​
4. Ni / Ni​+2​ ​ ​(0.10M) / Cu ​with the salt bridge ____________ V

​ ​(0.0020M) // Cu​+2​
5. Zn / Zn​+2​ ​ ​(0.10M) / Cu​​ with the salt bridge ____________ V

PROCEDURE - Part B – Constructing an Electrolytic Cell


1. Fill a plastic cup nearly-full with 0.50 M NaI​ solution.
​ Attach the clip to opposite sides of the
plastic cup. The tips of the clips should be touching the NaI solution.
2. Connect black wire to the negative terminal of a 9-volt battery. Then attach the red wire to the
positive terminal of the 9-volt battery. Note that the black wire is the negative electrode and the
red wire is the positive electrode
3. Observe the reaction for about 5 minutes. Write down a minimum of 5 observations. Write your
observations using complete sentences, please!

a)

b)

c)

d)

e)

4. Now place one drop of phenolphthalein into the middle of the plastic cup. Observe the reaction
and record your observations.

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CRITICAL THINKING

1. Based on your data, order the metals (Zn, Cu, Al, Ni), from most to least reactive. Explain your
reasoning.

2. Draw and label a picture of the following voltaic electrochemical cells for each of the following
half cells vs. the Cu​2+​ / Cu half-cell. (similar to Figure 1) Write the oxidation half-reaction,
reduction half-reaction, and net redox reaction. Indicate the direction of e​-​ flow. Calculate the
standard potential, E​o​cell​, for each of these electrochemical cells. Write the shorthand notation for
each cell.

a) Zn | Zn​2+

b) Ni​ ​/ Ni​2+

3.

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Write the net redox reaction for the following electrochemical cell.
​ ​(1.0M) // Cu​+2​
Zn / Zn​+2​ ​
​ (1.0M) / Cu

4. Calculate E​o​cell​ for the following electrochemical cell at 25​o​C.


​ ​(1.0M) // Cu​​+2​(1.0M)
Zn / Zn​+2​ ​
/ Cu

5. Use the Nearst Equation to calculate the theoretical voltage for the electrochemical cell at 25​o​C.
​ ​(0.10M) // Cu​+2​
Zn / Zn​+2​ ​ ​(0.10M) / Cu

6. Use the Nernst equation to calculate the theoretical voltage for the electrochemical cell at 25​o​C.
​ ​(0.0020M) // Cu​+2​
Zn/Zn​+2​ ​
​ (0.10M) / Cu

7. Calculate Gibb’s Free Energy, ​Δ​Go​​ , for the following cell at standard conditions.
​ ​(1.0M) // Cu​​+2​(1.0M)
Zn / Zn​+2​ ​
/ Cu ​cell

8. Calculate the equilibrium constant, K, for the following cell at standard conditions.
​ ​(1.0M) // Cu​​+2​(1.0M)
Zn / Zn​+2​ ​
/ Cu

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9. Draw a picture of the electrolytic cell you constructed using the battery and NaI solution. Label
the anode, cathode, the movement of ions to the electrodes. Write the oxidation half reaction,
reduction half-reaction, and net redox reaction for the cell.

10. Calculate E​o​cell​ for the above reaction at standard conditions.

11. Calculate the equilibrium constant, K​c​, ​ for


​ the above reaction at standard conditions.

12. Calculate ​Δ​Go​​ (KJ)​


​ for
​ the above reaction at standard conditions.

13. Why isn’t it possible to plate Na(s) in an electrolysis experiment with Na​+​(aq)?

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