Electrolysis Gases: dont conduct electricity except at high voltage Solid: only metals & graphite conduct Liquid:

Ionic substances conduct when molten or when in solution. Other liquids do not conduct, except mercury. The passage of current through compound decomposes it, this process called electrolysis & is special case of conduction Conductor: Solid substance that allow electricity to flow through them. All metals are good conductors of electricity. Non Conductor or Insulator: Substance that do not allow electricity to flow through them. All non- metals substance such as glass, plastic, wood & rubber are Insulator. Exception Carbon, in form of graphite is non metal but very good conductor of electricity.

Semi- conductor: substance which contain no free electrons & no io but allow very small curr to pass through them, th conduct weakly ex: silico

Electrolytes: Liquids that conduct an electric current. substance that contains ions which are free to move about, so they are ionic compounds that are molten or dissolved in water Ex: solution of acids & alkalis in water, soln of salts in water, molten salts (free moving ions)

Non-Electrolytes: Liquids that do not conduct an electric current. Covalent compounds such as ethanol, pure water or sugar solution. Ex: ethanol, petrol, sugar soln, pure wate oil

Electrolysis: is the decomposition of a substance by electricity/ passage of an electric current thro a liquid which itself decompose by current. conduction Electrolysis Substance carrying current is a solid, liquid Substance carrying current is liquid (or gas) Substance is decomposed by passage o Substance is not decomposed by current current Current can pass indefinitely Current will cease to flow when all compound has decomposed The following figure shows the apparatus could be used to see if a liquid is an electrolyte. Electrolysis takes place in the cell Lamp, if it glows, electricity must be flowing through the liquid Electrodes usually made of graphite or unreactive metal like platinum Electrodes are the electrical connection that carries the current into the liquid Anode is the +ve electrode Liquid under test called electrolyte, which is the liquid electrolyzed Mechanism: since current flows there must be a complete circuit. The current is carried bet the electrodes by movement of ions in the electrolyte. The driving force is the battery.

The electons Flow from Anode to Cathode in the external circuit. At Cathode: +ve ions gain electrons & become atoms or molecules (reduction) At Anode: -ve ions lose electrons & become atoms or molecules Electrolysis of molten NaCl (ionic compound) molten CaCl2 Molten KBr At cathode Na+ + e- -> Na 2Na+ +2 e- -> 2Na Ca 2+ + 2e- -> Ca 2K+ +2 e- -> 2K At Anode + Cl - - e- -> Cl 2Cl - - 2e- -> Cl2 Chlorine is diatomic so we cant write Cl only, should be Cl2 2Cl - - 2e- -> Cl2 2Br - - 2e- -> Br2

Electrolysis of molten lead bromide { PbBr2} Lead bromide wont conduct electricity when solid since no free ions, ions locked in a lattice. When is melted, ions come apart and free to carry current When the battery is connected, electrons are pumped from anode to cathode. Pb2+ ions migrate to cathode to undergo reduction. electrolyte At cathode At Anode + molten lead bromide Metallic lead (Pb) is Br- ions migrate to anode to undergo 2+ ions present: Pb , Br , produced. oxidation. 2+ BrPb + 2e -> Pb Bromide molecules (Br2) are produced. Drops of molten lead 2Br - -> Br2 + 2e- Or 2Br - - 2e- -> formed on cathode Br2 Due to the high temperature, Br2 escapes gas. Overall chemical equation PbBr2 (l) -> Pb (l) + Br2 (g) Ionic Equation Pb2+ (l) + 2Br- (l) -> Pb (l) + Br2 (g)

Electrolysis of Aqueous solution: It is difficult to predict the products of aqueous solution electrolysis than molten compounds. This because as well as there is cation & anion from salt, there is cation (H+) and anion(OH-) from wat Electrolysis of concentrated Aqueous Sodium Chloride: At cathode At Anode + From Na+ ClNaCl From H+ OHH2O

Only H+ takes part in electrolysis, H is lower in reactivity series than Na 2H+(aq) + 2e- ==> H2(g)

Only Cl- takes part in electrolysis, is in greater concentration than OH2Cl-(aq) ==> Cl2 + 2e-

The solution left containing sodium ions & hydroxide ions ( a solution of sodium hydroxide NaOH, solution is alkaline, turns red litmus paper blue) For dilute solutions of chloride, oxygen gas is produced at anode instead of Cl2 Electrolysis of Hydrochloric acid: electrolyte Concentrated hydrochloric acid
HCl(aq)

Aq CuSO4 Aq H2SO4

At cathode 2H+(aq) + 2e- ==> H2(g) Cu2+(aq) + 2e- ==> Cu(s) 4H+(aq) + 4e- ==> 2H2(g)

At Anode +
2Cl-(aq) - 2e- ==> Cl2(g) or 2Cl-(aq) ==> Cl2 + 2e4OH-(aq) - 4e- ==> 2H2O(l) + O2(g) 4OH-(aq) - 4e- ==> 2H2O(l) + O2(g)

Summary: Electrolysis of concentrated Aq NaCl At cathode At Anode + Hydrogen H2 Chlorine Cl2 The solution left is sodium hydroxide NaOH

Electrolysis of dilute Aq NaCl At cathode At Anode + Hydrogen H2 Oxygen O2 The solution of NaCl becomes more concentrated

Manufacture of Chlorine & Sodium Hydroxide: This method based on the electrolysis of concentrated aqueous sodium chloride (brine)

predict the products of aqueous solution: At cathode If the metal is higher than zinc in the reactivity series, then hydrogen gas is produced If the metal is zinc or lower than zinc in the reactivity series, then the metal is deposited formed At Anode + For concentrated solution of chlorides, chlorine gas is produced For dilute solution of chlorides, oxygen gas is produced For sulphates & nitrates, oxygen gas is produced

reactivity Most reactive

metal K Na Ca Mg Al Zn Fe Pb Cu Ag Au

Product at cath Above zinc, hydrogen gas i evolved at cath

Zinc and below metal deposite cathode

Electrolysis of Aquoeus copper II sulphate: using carbon electrode (inert) From CuSO4 From H2O At cathode Cu2+ H+ Only copper ions take part in the electrolysis Copper deposite on the cathode (as brown deposit) Cu2+(aq) + 2e- ==> Cu(s)

Least reactive

At Anode + SO42-

OHOnly OH- ions take part in electrolysis Oxygen gas is given off
4OH-(aq) - 4e- ==> 2H2O(l) + O2(g) or 4OH-(aq) ==> 2H2O(l) + O2(g) + 4e-

The solution left is dilute sulphuric acid ( H2SO4) , the solution changed from blue to colourless Summary: Electrolysis of Aqueous copper II sulphate At cathode At Anode + copper Oxygen The solution left is dilute sulphuric acid ( H2SO4) Ex: Electrolysis of Aqueous Zinc sulphate At cathode At Anode + Zinc Oxygen The solution left is dilute sulphuric acid ( H2SO4) Types of electrodes: Inert Carbon (graphite) or platinum, they dont take part in electrolysis. electrodes: Electrolyte only participates in the rn (Na+, Cl-, H+, OH-) At cathode 2H+(aq) + 2e- ==> H2(g) , At Anode 2Cl-(aq) - 2e- ==> Cl2(g) Active copper, silver, zinc & nickel. They take part in electrolysis & active metal anode electrodes: dissolves & soln doesnt participate, passes into solution as ions. In other words, mass of the active metal anode decreases Anode Cu(s) ==> Cu2+(aq) + 2e- & Cathode Cu2+(aq) + 2e- ==> Cu(s)

Electrolysis of Aqueous copper II sulphate: using copper electrode (active) Ions present: water provides few H+ & OH- ions. Copper sulphate provides Cu2+ & SO42- ions At cathode At Anode + (anode itself reacts) H+ & Cu2+ ions are attracted, since copper is lower in the Copper passes into solution as ions, th reactivity series, its ions are set free before hydrogen anode dissolves (decrease in mass, ions. Each copper ion receives 2 electrons & resulting thinner) copper atom is deposited Cu(s) ==> Cu2+(aq) + 2eCopper deposited (increase in mass, thicker) Cu2+(aq) + 2e- ==> Cu(s) The aqueous copper II sulfate remains unchanged, because the concentration of copper ions does not change, copper is transferred from anode to cathode Copper ions are produced at anode & deposited at cathode, the process will continue until anode is used up. Uses: Application of electrolysis: 1- Refining of copper: Copper can be refined by electrolysis using a block of impure copper as the anode & thin sheet of pure copper as the cathode. The electrolyte is aqueous copper II sulphate . Impurites sink to the bottom of container as anode sludge. The overall result is transfer of copper atoms from impure copper to the cathode. Electroplating

To purify impure 2- Electroplating Many metal objects are electroplated fo Protecting them from corrosion & rust Making them look attractive The aq soln contain ions of platting met

If copper is contaminated with other metals (except silver & gold) they will not undergo the transfer, since they are above copper in reactivity series. But if gold & silver are present with Cu will transfer before Cu as they are less reactive than Cu

Subject to be plated connected to cathode

plated with copper Silver nickel

Anode made from copper Silver nickel

electrolyte Aq CuSO4 Aq AgNO3 Aq Nickel sulphate

3- Extraction of metals: Reactive metals above zinc in reactivity series as Na, Mg,Ca, Al can be extracted only by electroly their molten compounds.

Extraction of Aluminium: Ore: Bauxite The purified bauxite (aluminium oxide - Al2O3) is electrolysed in molten Cryolite (Na3AlF6) Aluminiu oxide has too high melting point to be used on its own, so it dissolves in molten Cryolite at 900 C (Cryolite is used to lower MP of Al2O3), so reduce the amount of energy needed (reduce the cost)

At cathode At Anode + 3+ Al + 3e Al reduction. 2O2O2 - 4eoxidation. aluminium sinks to the bottom Oxygen gas is produced The hot oxygen escapes, it burns away the graphite anode C(s) + O2(g) CO2(g) thus have to b replaced from time to time Making aluminium is an expensive process because large amount of electricity are needed. The steel container is coated with carbon (graphite) and this is used as the negative electrode (cathode). Aluminium oxide (Al2O3) is an ionic compound. When it is melted the Al3+ and O2- ions are free to move and conduct electricity. Simple cell (Galvanic cell): The flow of electron was obtained from zn to Cu, as Zn is more active. It dissolves first & is considered as anode, it is ve pole because it is the source of electron Zn = Zn2+ + 2ewhile less active received electrons, so it is the +ve pole, also considered as cathode with respect to Zn

 Galvanic cell is a portable energy source (exothermic) Galvanic cell No battery More active dissolves & voltmeter indicates flow of electrons from more active to less active The more active is considered as the anode, which is ve pole source of electrons Electrolytic cell Battery present Flow of electrons is from anode to cathode anode +ve pole cathode -ve pole

In a galvanic cell, the current is produced by connecting an oxidation reaction to a reduction reaction in an electrolyte solution. Oxidation and reduction reactions or redox reactions, are chemical reactions involving a transfer of electrons from one atom in the reaction to another. When two different oxidation or reduction reactions are connected electrically, a current is formed. The direction depends on the type of reaction taking place at the terminal. Reduction reactions involve the gain of electrons. Electrons are needed to fuel the reaction and pulls these electrons from the electrolyte. Since electrons are attracted to the reduction site and current flows opposite the flow of electrons, current flows away from the reduction site. Since current flows from the cathode to the anode, the reduction site is the cathode.

Oxidation reactions involve the loss of electrons. As the reaction progresses, the oxidation terminal loses electrons Summary: to the electrolyte. Negative charge is moving away from the oxidation site. A positive current would move towards the oxidation site, against the flow Cathode - Since current flows to the anode, the oxidation site is the anode of b of electrons. Process Anode + electrodes Liquid the cell. electrol

Bromine & Lead Oxygen & hydrogen

Pb2+ + 2e- -> Pb (grey deposits) 2H+(aq) + 2e- ==>

2Br - -> Br2 + 2e- (red brown fumes)

4OH-(aq) - 4e- ==> 2H2O(l) + O2(g)

Graphite Graphite

Molten L Bromide Dilute

Anode dissolves & cathode grows Oxygen & Copper Bromine & Lithium

H2(g) (Bubbles) Cu2+(aq) + 2e- ==> Cu(s) (reddish brown deposit) Cu2+(aq) + 2e- ==> Cu(s) (reddish brown deposit) Li++ e- ==> Li

(Bubbles) Cu(s) ==> Cu2+(aq) + 2e- (copper from anode)

4OH-(aq) - 4e- ==> 2H2O(l) + O2(g)

Copper Carbon, graphite or Pt Graphite

sulphuric Copper sulphate

(Bubbles)

Copper sulphate

2Br - -> Br2 + 2e- (red brown fumes)

Molten L Bromide

Electrolysis Summary: Aqueous soln (ex salt sol in water) 4 ions formed From H+ OHwater From salt Na+ ClOne of them to One of them to anode cathode The preference depends on the position in electrochemical series, the lower the position the higher its preference to go to the electrode & so H+ goes to cathode & ClIn case of very dilute solution the most concentrated ions are preferred ex: dil HCl (H+,Cl-, H+, OH-) .;. H+, OH- not ClSummary: 1. All matels are good conductor in molten or solid state (Hg is a liquid metal) 2. All non- matels are non good conductor either in solid or molten state except carbon (graphite) 3. All ionic compounds are non conductors in solid state but conduct in molten or aqueous ex: NaCl, CuSO4, Na2O 4. All organic compounds are non- conductors ( ex: ethanol, sugar, petrol) except the ionic salts ex: sodium ethanoate.

Molten salt 2 ions only formed after me Ex: Molten NaCl Na+ ClEx: molten PbCl2 Pb2+ Cathode 2ClAnode