Chapter 6-Electrochemistry Electrolyte and Non-electrolyte 1.

Electrolytes are compounds which when molten or dissolved in water conduct electric current and are decomposed in the process. Example of electrolyte are acids, alkaline, salt solution or molten salts. All these are ionic substances. 2. A non-electrolyte is a liquid which does not allow the passage of electricity. Example of non-electrolyte are covalent substances which do not have ions.

3. Ionic compounds do not conduct electricity in the solid state because the ions are held in the lattice and do not move freely. 4. However, the ionic compounds will conduct electricity when they are melted or dissolved in water. This is because the ions are free to move in the molten state or aqueous solution.

5. Covalent compounds exist as molecules in organic solvents. Thus, they do not conduct electricity. However, HCl & NH3 in water conduct electricity. (i) HCl (l) + H2O(l) H3O+(aq) + Cl(aq) (ii) NH3(l) + H2O(l) NH4+(aq) + OH(aq) Electrolysis of Molten Compounds 1. Electrolysis is process whereby chemical substances are broken down into their constituent elements though usage of electricity 2. An electrolytic cell consists of a battery, an electrolyte that contains cation (positive ions), anions (negative ions) and two electrodes.

3. Electrode is conductor of electricity, carries electricity in & out during electrochemical process,
anode(-) & cathode(+).

4. Active electrode is an electrode which taken part in chemical reactions during electrolysis. Example: copper, silver and mercury electrode. 5. Inert electrode is an electrode which does not take part in chemical reaction during electrolysis. Example: Carbon and platinum electrode. 6. Anode is an electrode which is connected to positive terminal of the source of electricity in an electrolytic cell. 7. Cathode is an electrode which is connected to negative terminal of the source of electricity in an electrolytic cell. 8. Process of electrolysis involves 2 stages : (a) Movement of ions to electrodes Cations (+ve ions ) cathode (ve ) Anions (ve ions ) anode (+ve ) (b) Discharge of ions Cations discharged at the cathode by accepting e from cathode. Anions discharged at the anode by donating e to the anode. Electrons flow from anode to cathode through external circuit.

Half reaction method 1. Assign oxidation numbers to determine what is oxidized and what is reduced. 2. Write the oxidation and reduction half-reactions. 3. Balance each half-reaction. a. Balance elements other than H and O. b. Balance O by adding H2O. c. Balance H by adding H+. d. Balance charge by adding electrons. 4. Multiply the half-reactions by integers so that the electrons gained and lost are the same. 5. Add the half-reactions, subtracting things that appear on both sides. 6. Make sure the equation is balanced according to mass. 7. Make sure the equation is balanced according to charge.

Example: Electrolysis of molten lead (II) bromide

At the Cathode Observation When electricity is flowing, a silvery deposit of lead metal forms on the cathode. In fact, as it is molten, it is more likely to drip off in a molten blob.

At the Anode Observation When electricity is flowing, brown fumes of bromine gas are seen at the anode.

Half equation Pb2+ + 2e ---> Pb Explanation The lead(II) ions, as they are positive, move to the negative cathode, where each ion gains two electrons to form a lead atom. Any reaction at a cathode involved is again in electrons. This is called reduction or more exactly, cathodic reduction .

Half equation 2Br- ---> Br2 + e Explanation The bromide ions, as they are negative, move to the positive anode, where each loses an electron to form a bromine atom. Then two of these newly formed atoms combine to form bromine gas. Any reaction at an anode involves a loss of electrons.

Overall equation : Pb2+ + 2Br Br2 + Pb

Exercise 1 Electrolyte (molten) (i) Aluminium oxide Oxygen gas Half equation: .. (ii) Potassium iodide Iodine Half equation: (iii) Sodium chloride Chlorine gas Half equation: .. (iv) Zinc bromide Bromine gas Half equation: .. Substance discharged at the electrodes and the half equation Anode Cathode Aluminium Half equation: .. Potassium Half equation: .. Sodium Half equation: . Zinc Half equation: .

Electrolysis of Aqoueous Solutions 1. Aqueous solution of a compound is a solution produced when the compound is dissolved in water. 2. An aqueous solution contains (a) anion and cation of the compound (b) H+ and OH- from partial dissocation of water 3. Two cation (one from the compound and H+) will move toward cathode and two anion (one from compound and OH-) will move toward anode. 4. Only one type of cation and anion will be selected to be discharged at cathode and anode. 5. The selective discharge of ions depends on three factors: a. Ions Position in electrochemical series b. Ions concentration of electrolytes c. Type of electrodes used in electrolysis

A. Position in electrochemical series Electrochemical Series

Easier to discharge

1. The electrochemical series is a list of ions arranged ascending order of their tendency to discharged. 2. The lower the position of an ion in the electrochemical series, the higher is the tendency of the ions to be discharged. Example: Electrolysis of Aqueous Sulphuric Acid

1. As sulphuric acid is aqueous, it is composed not only of hydrogen ions (H+ ) and sulphate ions
(SO4 ), but also of hydroxide ions (OH ) from the water. 2. The apparatus that shown above is used to carry out this electrolysis and collect the gases given off. 3. When we have more than one type of ion moving to an electrode, selective discharge (or preferential discharge) takes place. 4. This means that the ion which can lose or gain electrons with the greatest ease is discharged, and the other ions, which are harder to discharge, remain in solution. 5. With the electrolyte aqueous sulphuric acid, migration of ions to the electrodes also occurs. At the Cathode Here we have only one ion, the hydrogen, H+ (aq), and each ion gains an electron to become a hydrogen atom. At the Anode Here we have a choice of either 2sulphate, SO4 (aq), or hydroxide OH (aq) ions. Hydroxide is easier to discharge, so
2-

Two of these newly formed atoms then combine to form a hydrogen gas molecule.

oxygen gas is given off at the anode.

Equation: 2H + 2e ---> H2
+

Equation: OH- + 4e ---> O2 + H2O

Exercise 2 The diagram below shows the set-up of apparatus of an electrolytic cell containing concentrated copper(II) sulphate solution. Two test tubes filled with copper(II) sulphate solution were placed over the electrodes J and K to collect any gas evolved. The switch is then turned on so that electrolysis of copper(II) sulphate solution can occur.

(a) Identify the cations and the anions present in the aqueous solution. Cations: .. Anions: .. (b) Identify which electrode ( J or K ) is the anode and the cathode: Anode .. Cathode . (c) (i) Which ion is selectively discharge at the anode? (ii) Give a reason for your answer in (c) (i). .. ... (iii) What do you observe at the anode? (iv) Give one test to confirm the gas released at K. . (v) Write a half equation to represent the discharge of ions at anode. . (d) (i) Which ion is selectively discharge at the cathode? (ii) Give a reason for your answer in (d) (i) .

(iii) Which do you observe at the cathode? (iv) Write a half equation to represent the discharge of ions at the cathode. . . (e) What do you observe about the copper(II) sulphate solution? ..

B. Ions concentration of electrolytes Example: Electrolysis of dilute sodium chloride solution and concentrated sodium chloride Dilute sodium chloride solution Anions : OH- and ClOH- ions are selectively discharge according to the position of ions in the Electrochemical Series, ES. Gas bubbles are formed which lighted up a glowing wooden splinter. This gas is oxygen. 4OH- ---> 2 H2O + O2 + 4e Cations : H+ dan Na+ H+ ions are selectively discharge according to the position of ions in the ES. Gas bubbles are formed. When a lighted wooden splinter is placed near the mouth of the test tube, a pop sound is produced. Hydrogen gas is produced 2H+ + 2e ---> H2 Concentrated sodium chloride solution Anions : OH- and ClCl- ions are discharged instead of OHbecause of their higher concentration in the electrolyte. A greenish-yellow gas with a pungent and choking smell is released. The gas turns the blue litmus paper red and then white. 2Cl- ---> Cl2 + 2e

At Anode

At Cathode

Cations : H+ dan Na+ H+ ions are selectively discharge according to the position of ions in the ES. Gas bubbles are formed. When a lighted wooden splinter is placed near the mouth of the test tube, a pop sound is produced. Hydrogen gas is produced 2H+ + 2e ---> H2

** The higher the position in the electrochemical series are very stable (remain as cation or anion). For example NO3- ions, OH- ions, Na+ ions and K+ ions, the concentration factor is unimportant. In this case, OH- and H+ ions are selectively discharged even though their concentrations are very low.

C. Type of electrodes used in electrolysis Example: Electrolysis of copper(II) sulphate using Carbon electrode Vs Copper electrodes Carbon Electrode Anions: OH- and SO4OH- ions are selectively discharge according to the position of ions in the Electrochemical Series, ES. Gas bubbles are formed which lighted up a glowing wooden splinter. This gas is oxygen. At Cathode 4OH- ---> 2 H2O + O2 + 4e Cations : H+ dan Cu2+ Cu2+ ions are selectively discharge according to the position of ions in the ES. The intensity of the blue colour of electrolyte decrease as the concentration of copper(II) ion is decreases when more copper is deposited at cathode. 2 Cu2+ (aq) + 2e ---> Cu (s) Copper Electrode Anions: OH- and SO4The OH- and SO4- are not discharged. Instead, the copper electrode dissolves to form copper(II) ions. Cu (s) --> 2 Cu2+ (aq) + 2e

At Anode

Cations : H+ dan Cu2+ Cu2+ ions are selectively discharge according to the position of ions in the ES. The intensity of the blue colour of electrolyte remain unchanged as the concentration of copper(II) ions is remains unchanged. 2 Cu2+ (aq) + 2e ---> Cu (s)

** The factors that affect the electrolysis:

Main factor: Position of ions in the electrochemical series Second factor: Concentration of the electrolyte Third factor: Types of electrode as anode

Exercise 3: The table below shows three electrolytic cells with different electrolytes and different electrodes. You are required to answer each section by writing your answer in the spaces provided.

Summary of Electrolysis