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



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


Electrolytic cell

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



 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.



 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.



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


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)

© MHS 2009


Example 1. Battery + ammeter A + cathode / -ve electrode 2+ - - cathode / -ve electrode 2Br. Battery + ammeter A + anode / +ve electrode - 2. Br2 + 2e- Pb + 2e  Pb anode / +ve electrode anion/ -ve ion - + cation/ +ve ion anion/ -ve ion - cation/ + +ve ion Molten PbBr2 Molten NaCl © MHS 2009 2 .

3. © MHS 2009 3 . H2O H+ + OH There are three factors that may influence the selective discharge of ions during the electrolysis of an aqueous solution. i. and 2 types of anions (anions of the salt and hydroxide ions. ZnI2 + cation/ +ve ion Molten lead (II) oxide 9. H+).are always present together with the ions produced from the dissociation of salts in aqueous solutions. 4. Position of ions in the electrochemical series The ions that are lower in the electrochemical series will be selectively discharged - . 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.  This is because water dissociates partially to form H+ and OH-. OH-).  H+ and OH.  An aqueous solution of a salt consists of 2 types of cations (cations of the salt and hydrogen ions. Electrolysis of Aqueous Solutions  An aqueous solution is produced when a solute is dissolved in water.

both SO42. © MHS 2009 6. iii.ions are not discharge. 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.ion in the electrochemical series.ii. OH. the mass of anode decrease.ions and OH. Cu2+. 1. the ions is selectively discharged.  Copper acts as an active electrode here because it takes part in the chemical reactions during electrolysis. Hence.ions are discharged at the anode because of the position of OH. ZnI2 solution 5.  If copper is used as the anode. Battery + ammeter A + anode / +ve electrode cathode / -ve electrode - 4. Concentration of ions in the electrolytes If the concentration of a particular ion is high. Types of electrodes used in the electrolysis  The common materials used as electrodes are carbon and platinum because they are inert.  Instead the copper anode dissolves by releasing electrons to form copper (II) ions. Battery + ammeter A + anode / +ve electrode cathode / -ve electrode ammeter A + anode / +ve electrode cathode / -ve electrode 2. CuSO4 solution. Battery + - anion/ -ve ion - + cation/ +ve ion anion/ -ve ion - + cation/ +ve ion Dilute copper (II) chloride CuCl2 Silver nitrate. CuSO4  Cu2+ + SO42H2O H+ + OH If carbon is used as the electrodes. 4 . AgNO3 solution 3.  Example: Electrolysis of copper (II) sulphate.

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 - Ag  Ag + e anion/ -ve ion + Ag + e  Ag Ag C cation/ +ve ion anion/ -ve ion - + - Ni Ni + cation/ +ve ion - + Ag2SO4 NiSO4 10 Electrolysis in Industries © MHS 2009 5 . Battery + ammeter A + anode / +ve electrode cathode / -ve electrode - Concentrated copper (II) bromide. CuBr2 8.

11 Voltaic Cells © MHS 2009 6 . Al2O3 using carbon electrodes. electrolysis is used to coat one metal onto another metal. 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. In the purification of copper. Al2O3 to lower its melting point. Aluminium can be extracted from its ore. Na3AlF6 is added to aluminium oxide.Extraction of metals Reactive metals such as aluminium and magnesium can be extracted from their ores be electrolysis. Electroplating of metals In electroplating of metals. the impure copper is made to be the anode while the cathode is a thin layer of pure copper. In this process. molten aluminium oxide. Purification of metals Pure copper and silver can be obtained through the process of electrolysis. a substance known as cryolite. In the process of electroplating.

A simple voltaic cell consists of two different metals immersed into an electrolyte. Each electrode is immersed into a different electrolyte..The electron flow form negative terminal to positive terminal.The less electropositive metal (metal that is lower position in the ECS) will be positive terminal. to allow the flow of ions so that the circuit is completed ii. Cation which is lower at ECS will be discharged. The porous pot and salt bridges are: i. to prevent the two aqueous solution from mixing 12 The Electrochemical Series (ECS) © MHS 2009 7 . zinc and copper are used as electrodes.The more electropositive metal (metal that is higher position in the ECS) will release electron  Negative terminal . The electrolytes are connected by a salt bridge or a porous pot. Chemical energy is converted to electrical energy in the cell. 12 Daniell Cell In a Daniell cell. . .

It is also used to predict the ability of one metal to displace another metal from its salt solution.- The electrochemical series is an arrangement of metals based on the tendency of each metal atom to donate electrons.portable  Spillage of acid can occur  Big in size  Heavy. - 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 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 . 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 © MHS 2009 Voltaic cell 8 . - The electrochemical series is used to determine the terminals and voltage of a cell. the greater the voltage produced by the cell. - The further the two metals are in the ECS.

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) © MHS 2009 9 .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.