Experiment 2: Electrolytic Cell-Electrolysis of Aqueous Solution

Introduction Electrolysis is the process of electrical energy is used to cause a nonspontaneous chemical reaction to occur. The electrolytic cell as shown in Figure 1 is an apparatus for performing electrolysis. The electrolytic cells consist of power supply such as battery to provide energy to transfer electrons from anode to cathode. In electrolysis cell, reduction occurs at cathode while oxidation occurs at anode. In Molten Sodium Chloride, the cations are Na+ and the anions are Cl- ion. This process is used to produce chlorine gas. The reaction occurs are; : 2Cl-1(l) Cl2(g) + 2e : 2Na+(l) + 2Cl-1(l) Cl2(g) + 2Na(l)

Anode (oxidation)

Cathode (reduction) : 2Na+(l) + 2e 2Na(l) Overall reaction

However, aqueous sodium chloride solution contains water which indicates several species that cloud be oxidized and reduced. The main purpose of this experiment is to know which ions will oxidize or reduce with the present of water based on it electrochemical negativity and also others factor such as application of over voltage.

Figure 1 : Electrolysis Cell Objectives

The intentions of this experiment are:i. to identify the reactions occurring at the anode and cathode during the electrolysis of various aqueous salt solutions ii. iii. to observe the electrolysis of water and the gases liberated at the electrodes and to study the suitable electrode and aqueous solution for water splitting process.

Materials and Apparatus The lists of materials and apparatus used are:i. ii. iii. iv. v. vi. vii. Carbon/Graphite rods Copper plates 100 mL beaker Power supply Two electrical wires (different color) that attached to crocodile clips Cardboard with two holes Litmus paper (blue)

Chemicals The lists of chemicals used are:i. ii. iii. iv. NaCl solution NaBr solution Na2SO4 solution Phenolphthalein indicator

Procedure

Procedure Overview The resulted products from the electrolysis of various salt solutions was observed and identified.

1. Set Up the Electrolysis Apparatus The Electrolytic Cell apparatus was set up as in Figure 1. The crocodile clips were connected to the responding electrodes, listed in Table 1.

2. Electrolyze the solutions

A solution from Table 1 was filled in beaker until three-froths full and 10 drops of phenolphthalein were added in the solutions. The suggested electrode in Table 1 was immersed into the solutions. The solutions were electrolyzed at 6V for 5 minutes. The changes at the solutions, electrodes and the gas evolved were observed and recorded.

No. 1. 2. 3. 4. 5. 6.

Solution Distilled Water 0.001M NaCl 0.5M NaCl 0.5M NaBr 0.5M Na2SO4 0.5M Na2SO4

Electrodes(Anode and Cathode) Carbon(Graphite) Carbon(Graphite) Carbon(Graphite) Carbon(Graphite) Polished Copper Metal Strips Carbon(Graphite) Table 1

Results and Analysis

Electrodes No. Solution (Anode and Cathode) 1 Distilled Water 0.001 M NaCl Carbon/Carbon Carbon/Carbon Anode Cathode Anode Cathode

Observations

No change No change No change Light purple color appear

Litmus paper No change The colorless solution turned to light purple upon the addition of phenolphthalein Anode Cathode Light purple purple

Solution 3 0.5 M NaCl Carbon/Carbon

No change Gas evolve

Litmus paper Blue red 4 0.5 M Carbon/Carbon Solution The colorless solution turned to light

NaBr Anode Cathode Odor

pink upon the addition of phenolphthalein Light pink purple

Solutions changes to light brown Gas evolve Pungent smell The colorless solution turned to purple upon the addition of

0.5M Na2SO4

phenolphthalein Carbon/Carbon Anode Cathode purple purple (no change)

Bubbles slower Bubbles faster The colorless solution turned to purple upon the addition of

0.5M Na2SO4

Copper/Copper Anode Cathode Table 2

phenolphthalein purple purple (no change)

No change No change

Electrolyte Solution

Dissociation of Electrolytes

Expectation of selected ion and product Ions migrating to cathode: Na+, H+ Ions discharged at cathode: H+

Na+ + e- Na NaCl (Dilute) Cl2(g) + 2 e2ClO2 + 4 H+ + 4 e- 2 H2O 2H2O + 2e H2 + 2OH-

Product at cathode: H2 gas Ions migrating to anode: Cl-, OHIons discharged at anode: OHProduct at anode: O2 gas Ions migrating to cathode: Na+ , H+

NaCl (Concentrated)

Na+ + e- Na Cl2(g) + 2 e2Cl-

Ions discharged at cathode: Na+ Product at cathode: H2 gas

O2 + 4 H+ + 4 e- 2 H2O 2H2O + 2e H2 + 2OHIons migrating to anode: Cl-, OHIons discharged at anode: ClProduct at anode: Cl2 gas Ions migrating to cathode: Na+, H+ Ions discharged at cathode: Na+ Na+ + e- Na NaBr Br2 + 2 e 2 Br
-

Product at cathode: H2 gas Ions migrating to anode: Br- ,OHIons discharged at anode: BrProduct at anode: Br2 Ions migrating to cathode: Na+ , H+ Ions discharged at cathode: H+

O2 + 4 H+ + 4 e- 2 H2O 2H2O + 2e H2 + 2OH-

Na+ + e- Na Na2SO4 S2O82- + 2 e- 2 SO42O2 + 4H+ + 4 e- 2 H2O 2H2O + 2e H2 + 2OH-

Product at cathode: H2 Ions migrating to anode: SO42- ,OHIons discharged at anode: OHProduct at anode: O2

Discussions: In the electrolysis process, the ions dissociated would determine which ions will be discharged according to the electrochemical series. From the observation, blue litmus paper change to red color in the electrolysis of concentrated aqueous sodium chloride indicated that gas produced at anode was Cl2 gas not O2. This phenomenon happens due to application of overvoltage during performing this analysis. Higher voltage was applied because Cl 2 gas is more easily reduced than O2.that it would be more difficult to oxidize Cl- than H2O. The pungent smell produced in the electrolysis of an aqueous Sodium bromide indicates the product at anode is bromine gas. In the electrolysis of an aqueous sodium sulfate, halide ions are reducing at cathode and OH- is oxidizing at anode. SO42- is the best anion that the most difficult anion to oxidize. The most suitable electrode and aqueous solutions for water splitting process are Copper/Copper and Na2SO4 respectively.

Conclusions 1. The reactions occurring at the anode and cathode during the electrolysis of various aqueous salts was identified. Water is present in aqueous solution; the ions dissociated would determine which ions will be discharged according to the electrochemical series. 2. Due to the electrochemical series, the most suitable electrode and aqueous solutions for water splitting process are Copper/Copper and Na2SO4 respectively.

Questions

1. Would solid NaCl conduct electricity? Why did the salt make the water more conductive to electricity? No, Solid NaCl (salt) do not have free electron to allow electric current to pass through the substances. In the presence of water and when a voltage is applied, it aids the salt to let the ions to be free, thus they are more in response to an electric field which makes NaCl to be able to conduct electricity.

2. What gases were formed at anode and cathode in beaker containing 0.5M NaCl? Write the half-reaction that occurred in this beaker. Anode: 2H2O + 2e H2 + 2OH-, gas evolved: H2 gas. Cathode: Cl2(g) + 2 e2Cl-, gas evolved: Cl2.

3. What was the purpose of adding phenolphthalein to the solution? As an indicator which enables any changes to be observed.

4. If copper electrodes had been used instead of the carbon electrodes for the electrolytic cells, the observed reactions may have been different. Why? Carbon electrode is an inert electrode, thus it will not compete with the ions present in the solutions. By replacing carbon with copper which is not an inert electrode, it will undergo erosion or electrodeposition instead of producing gas at the electrode.

5. Why does more gas form at one electrode than at the other electrode for the electrolysis of 0.5M Na2SO4 solution? Anode: O2 + 4 H+ + 4 e- 2 H2O

Cathode: 2H2O + 2e H2 + 2OHAt cathode, reduction occurs and the H2 gas is evolved while at anode, oxidation takes place.

6. In the electrolysis of an aqueous salt solution, the nitrite ion NO3- , migrates to the anode. Considering that the nitrogen in the NO3- (aq) is at its maximum oxidation state (of +5), what electrolysis products(s) might you expect to observe at the anode? Based on the electrochemical series, NO-3 wont be discharge because it is located at the upper top while OH- located at the bottom. Hence, expected product would be oxygen gas. O2 + 4 H+ + 4 e- 2 H2O

7. Calculate the volume of gases that will be collected at anode and cathode when an aqueous solution of Na2SO4 is electrolyzed for 2 hours with a 10A current. Cathode (reduction): 2H2O + 2e H2 + 2OH- (x2) Anode (oxidation) : 2 H2O O2+ 4H+ 4 e Overall: 2H2O 4H2 + O2 From oxidation: 1 mol O2 = 4e Q = It = (10)(2x60x60) = 72000C Q = mnF = (4)(n)(96500) m = 0.1865 mol volume of gas = no. of mol x 24L = 0.1865 x 24 = 4.4L

From reduction Q = (2)(n)(96500) m = 0.3731 mol volume of gas = no. of mol x 24L = 0.3731 x 24 = 8.95 L

8. Describe in your own words the whole process of electrolysis of water from your findings (including the electrochemical reactions occur at both electrodes, the suitable electrode and electrolyte used). The electrolysis of water is considered a well-known principle to produce oxygen and hydrogen gas, There must be no unwanted gas evolved such as bromine or chlorine gas occurs. Due to the electrochemical series, the most suitable electrode and aqueous solutions for water splitting process are Copper/Copper and Na2SO4 respectively. Halide ions are reducing at cathode and OH- is oxidizing at anode. SO42- is the best anion that the most difficult anion to oxidize.

References C.Raymon, , M.S.A.M.S.Azyze.,G.F.Chuen.,M.A.Salwana., Ghazali.N., Ramli.S., (2005)Physical Chemistry for Matriculation, revised ed., McGraw-Hill Malaysia, page 359365