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Chapter 6: Electrochemistry

1. Electrolyte Electrolytes are substances in molten state or aqueous solution that can conduct electricity due to the presence of free moving ions 2.
Non-electrolytes

Non-electrolytes are substance that cannot conduct electricity either in molten state or aqueous solution.

3.

Electrolysis

Electrolysis is a process whereby compounds in molten or aqueous state are broken down into their constituent elements by passing electricity through them.

4.

Electrolytic cell

The electrolytic cell is the set of apparatus needed to conduct electrolysis. It consists of a battery, an electrolyte and two electrodes.

5.

Electrode

Electrodes are electrical conductors. Graphite or platinum is usually used as electrodes because they are inert, they do not react with electrolyte or the products of electrolysis.

6.

Anode

The electrode which is connected to the positive terminal of an electric source. Negatively charged ions (anions) in the electrolyte are attracted to the anode.

7.

Cathode

The electrode which is connected to the negative terminal of the batteries. Positively charged ions (cations) in the electrolyte are attracted to the cathode.

8.

Electrolysis of Molten Compounds

Molten compound: A molten compound consists of one type of cations and one type of anion only. In solid state, ions do not move freely but are held in fixed positions in a lattice. In molten electrolyte, the ions move freely. During electrolysis, the negative ions or anions move to the anode. The positive ions or cations move to the cathode. A new substance is then formed at each electrode. Example: Electrolysis of molten lead (II) bromide, PbBr2. PbBr2 is an ionic compound. It consist Pb2+ and Br-. In solid PbBr2, these ions do not move freely but are held in fixed positions in a lattice. When it melts, the ions are free to move. During the electrolysis of molten PbBr2, Br- are attracted to the anode. At the anode, Br- undergo discharge whereby each of these ions releases an electron to form a neutral bromine atom. Two bromine atoms combine to form a bromine gas, Br2 molecule. Thus, Br2 is released at the anode. Half equation: 2Br-(l) Br2(g) + 2e At the cathode, Pb2+ undergo discharges whereby each of the ions accepts two electrons to form a lead atom. Thus, lead metal is formed at the cathode. Half equation: Pb2+(l) + 2e- Pb(s) Combining the two half equations, we get the overall equation. Pb2+(l) + 2Br-(l) Pb(s) + Br2(g)

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Example 1.
Battery + ammeter A + anode / +ve electrode -

2.
Battery + ammeter A +
cathode / -ve electrode
2+ -

cathode / -ve electrode

2Br- Br2 + 2e-

Pb

+ 2e Pb

anode / +ve electrode

anion/ -ve ion

cation/ +ve ion

anion/ -ve ion

cation/ + +ve ion

Molten PbBr2

Molten NaCl

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3.

4.

Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

anion/ -ve ion

cation/ + +ve ion

anion/ -ve ion Molten zinc iodide, ZnI2

cation/ +ve ion

Molten lead (II) oxide

9.

Electrolysis of Aqueous Solutions An aqueous solution is produced when a solute is dissolved in water. An aqueous solution of a salt consists of 2 types of cations (cations of the salt and hydrogen ions, H+), and 2 types of anions (anions of the salt and hydroxide ions, OH-). H+ and OH- are always present together with the ions produced from the dissociation of salts in aqueous solutions. This is because water dissociates partially to form H+ and OH-. H2O H+ + OH There are three factors that may influence the selective discharge of ions during the electrolysis of an aqueous solution. i. Position of ions in the electrochemical series The ions that are lower in the electrochemical series will be selectively discharged

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ii. iii.

Concentration of ions in the electrolytes If the concentration of a particular ion is high, the ions is selectively discharged. Types of electrodes used in the electrolysis

The common materials used as electrodes are carbon and platinum because they are inert. Example: Electrolysis of copper (II) sulphate, CuSO4 solution. CuSO4 Cu2+ + SO42H2O H+ + OH If carbon is used as the electrodes, OH- ions are discharged at the anode because of the position of OH- ion in the electrochemical series. If copper is used as the anode, both SO42- ions and OH- ions are not discharge. Instead the copper anode dissolves by releasing electrons to form copper (II) ions, Cu2+. Hence, the mass of anode decrease. Copper acts as an active electrode here because it takes part in the chemical reactions during electrolysis. 1.
Battery + ammeter A + anode / +ve electrode cathode / -ve electrode ammeter A + anode / +ve electrode cathode / -ve electrode

2.

Battery + -

anion/ -ve ion

cation/ +ve ion

anion/ -ve ion

cation/ +ve ion

Dilute copper (II) chloride CuCl2

Silver nitrate, AgNO3 solution

3.
Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

4.
Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

anion/ -ve ion

cation/ +ve ion

anion/ -ve ion

cation/ +ve ion

Copper (II) sulphate, CuSO4 solution

Zinc iodide, ZnI2 solution

5.
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6.

Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

anion/ -ve ion

cation/ +ve ion

anion/ -ve ion

cation/ +ve ion

Concentrated potassium chloride, KCl


7.
Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

Concentrated copper (II) bromide, CuBr2


8.
Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

Ag Ag + e
anion/ -ve ion

Ag + e Ag Ag C
cation/ +ve ion
anion/ -ve ion -

Ni

Ni
+

cation/ +ve ion

Ag2SO4

NiSO4

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Electrolysis in Industries

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Extraction of metals Reactive metals such as aluminium and magnesium can be extracted from their ores be electrolysis. Aluminium can be extracted from its ore, molten aluminium oxide, Al2O3 using carbon electrodes. In this process, a substance known as cryolite, Na3AlF6 is added to aluminium oxide, Al2O3 to lower its melting point.

Purification of metals Pure copper and silver can be obtained through the process of electrolysis. In the purification of copper, the impure copper is made to be the anode while the cathode is a thin layer of pure copper.

Electroplating of metals In electroplating of metals, electrolysis is used to coat one metal onto another metal. In the process of electroplating, a more expensive or attractive metal such as silver or gold is coated onto the object to make it look more attractive and more resistant to corrosion.

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Voltaic Cells

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- A simple voltaic cell consists of two different metals immersed into an electrolyte. Chemical energy is converted to electrical energy in the cell. - The more electropositive metal (metal that is higher position in the ECS) will release electron Negative terminal - The less electropositive metal (metal that is lower position in the ECS) will be positive terminal. - The electron flow form negative terminal to positive terminal. Cation which is lower at ECS will be discharged.

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Daniell Cell In a Daniell cell, zinc and copper are used as electrodes. Each electrode is immersed into a different electrolyte. The electrolytes are connected by a salt bridge or a porous pot. The porous pot and salt bridges are: i. to allow the flow of ions so that the circuit is completed ii. to prevent the two aqueous solution from mixing

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The Electrochemical Series (ECS)

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The electrochemical series is an arrangement of metals based on the tendency of each metal atom to donate electrons.

The electrochemical series can be constructed based on the potential difference between two metals, and the ability of a metal to displace another metal from its salt solution.

The electrochemical series is used to determine the terminals and voltage of a cell. It is also used to predict the ability of one metal to displace another metal from its salt solution.

The further the two metals are in the ECS, the greater the voltage produced by the cell.

The Advantages Disadvantages of Various Voltaic Cells Cell Daniell cell Advantages Easily set up in the laboratory Disadvantages Wet cell electrolyte easily split Voltage cannot last Dry cell No spillage Small in size Easily carried about Produces regular current and voltage Obtained in different sizes Alkaline cell Lasts longer than dry cell (10 x) Produces a higher and more regular current Leakage can occur if cell cannot be used anymore Expensive Cannot be recharged Mercury cell Small in size Produces regular current for a longer period of time Lasts a long time Lead-acid accumulator Can be recharged Produces a high voltage (12V) for a long period time Produces a high current (175A) suitable for a heavy duty Nickelcadmium cell Can be recharged up to 500 times Dry cell no spillage Smaller than accumulator - portable Spillage of acid can occur Big in size Heavy, difficult to be carried about Expensive Loses charge if not used for long Expensive Transformer needed for recharging cell Very expensive Cannot be recharged Mercury that is produced is poisonous Does not last Cannot be recharged Leakage can occur if cell cannot be used anymore

Electrolytic cell
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Voltaic cell

Battery + ammeter A + anode / +ve electrode cathode / -ve electrode -

anion/ -ve ion

cation/ + +ve ion

Similarities Contains an electrolyte Consist of an anode and a cathode Electron move from the anode to the cathode in the external circuit (connecting wires) Positive ions and negative ions move in the electrolyte Chemical reactions involve the release or acceptance of electrons Differences Characteristics Energy change Electric current and reaction Electrode / Terminal Flow of electron Electrolytic Cell Electrical energy chemical energy Electric current results in a chemical reaction Cathode: Negative terminal Anode : Positive terminal Electron flow from the positive electrode (anode) to the negative electrode (cathode) Negative terminal Cation receives electrons from the cathode (negative terminal) Positive terminal Anion release electrons to the anode (positive terminal) Types of electrodes Same or two different types of metal, or graphite electrodes Electron are released at the negative terminal Electrons are received by the positive terminal Two different types of metal Voltaic Cell Chemical energy electrical energy Chemical reaction produces an electric current Cathode: Positive terminal Anode : Negative terminal Electrons flow from the negative electrode (anode) to the positive electrode (cathode)

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