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Chapter 12

CHAPTER 12 : OXIDATION & REDUCTION

REDOX REACTIONS
1.1 The meaning of REDOX reaction 1. REDOX reaction A reaction where both oxidation and reduction occur at the same time. 2. Oxidation and reduction can be defined in four ways : OXIDATION (i) Loss of oxygen and gain in oxygen Gain of oxygen REDUCTION Loss of oxygen Example :

2Mg + O2 2MgO CuO + H2 Cu + H2O N2 + 3H2 2NH3 Mg Mg2+ + 2e Cl + e ClZn + Cu2+ Zn2+ + Cu

(ii) Loss of hydrogen and Loss of hydrogen gain in hydrogen (iii) Loss of electrons and gain in electrons (iv) Change in oxidation Loss of electron Increase in oxidation number

Gain of hydrogen

Gain of electron Decrease in oxidation number

number

3. (i) Oxidizing agent : a substance that oxidized another substance. the oxidizing agent is reduced in the process. (ii) Reducing agent : a substance that reduced another substance. the reducing agent is oxidized in the process. 1.2 Example of REDOX reactions (i) In terms of gain/loss of oxygen Example 1 : Magnesium is oxidised (gain of oxygen)

Mg

CuO

MgO +

Cu

Copper(II) oxide is reduced (loss of oxygen) Explanation : Magnesium, Mg gains oxygen and it is oxidized. Magnesium has reduced copper(II) oxide, CuO. Magnesium, Mg is reducing agent. Copper(II) oxide , CuO loses oxygen and it is reduced. Copper(II) oxide has oxidized magnesium, Mg. Copper(II) oxide is oxidizing agent.

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(ii) In terms of gain/loss of hydrogen Example 2 : Hydrogen sulphide is oxidised (loss of hydrogen)

H2S +

Cl2

2HCl

Chlorine is reduced (gain of hydrogen) Explanation : Hydrogen sulphide, H2S loses hydrogen and it is oxidized. Hydrogen sulphide, H2S has reduced chlorine, Cl2. Hydrogen sulphide, H2S is reducing agent. Chlorine, Cl2 gains hydrogen and it is reduced. Chlorine, Cl2 has oxidized hydrogen sulphide, H2S. Chlorine, Cl2 is an oxidizing agent.

Example 3 : Copper(II) oxide is reduced (loss of oxygen)

3CuO +

NH3

3Cu

3H2O

N2

Ammonia is oxidised ( loss of hydrogen) Explanation : Copper(II) oxide, CuO loses oxygen and it is reduced. Copper(II) oxide, CuO has oxidized ammonia, NH3. Copper(II) oxide, CuO is oxidizing agent. Ammonia, NH3 loses hydrogen and it is oxidized. Ammonia, NH3 has reduced copper(II) oxide. Ammonia, NH3 act as reducing agent.

(iii) In terms of gain/loss of electron Example 4 :

(i)

NaCl is an ionic compound. It exist as Na+ ions and Cl- ions. NaCl Na+ + Cl-

2Na

Cl2

(ii)

2NaCl

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Explanation :
(i)

Sodium, Na with an electron arrangement of 2.8.1 loses an electron to form sodium ion, Na+ in sodium chloride, NaCl. Sodium is oxidized.

Na

Na+

(ii) Chlorine, Cl2 gains electrons to form chloride ions. Cl- in sodium chloride, NaCl. Chlorine is

reduced.

Cl2 + 2e

2Cl-

Sodium, Na has reduced chlorine, Cl2. Sodium, Na is a reducing agent. Chlorine, Cl2 has oxidized sodium, Na. Chlorine, Cl2 is an oxidizing agent. MgSO4 is an ionic compound. It exist as Mg2+ ions and SO42- ions. Example 5 : MgSO4 Mg2+ + SO42(i)

Mg

CuSO4
(ii)

MgSO4

Cu

Explanation :
(i)

Magnesium atom, Mg loses two electrons to form magnesium ion, Mg2+.

Mg
(ii)

Mg2+

+ 2e

Magnesium is oxidized. Copper(II) ion, Cu2+ gains two electrons to form copper atom, Cu.

Cu2+ + 2e

Cu

Copper(II) ion, Cu2+ is reduced.

Magnesium, Mg has reduced copper(II) ion, Cu2+. Magnesium, Mg is a reducing agent. copper(II) ion, Cu2+ has oxidized Magnesium, Mg. copper(II) ion, Cu2+ is an oxidizing agent.

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(iv) In terms of change in oxidation number General rules to determine Oxidation Number 1. The oxidation number of atoms and molecules of elements is zero. Example : Atom of Element Copper, Cu Sodium, Na Iron, Fe Helium,He Molecule of Element Hydrogen gas, H2 Oxygen gas , O2 Chlorine gas, Cl2 Oxidation number 0 0 0 0 Oxidation number 0 0 0

2. The oxidation number for hydrogen in most of its compound is +1.

H
Hydrogen atom Oxidation number 0

H2
Hydrogen molecule 0

HCl
Hydrogen ion

+1

3. The oxidation number for oxygen in most of its compound is -2.

O
Oxygen atom Oxidation number 0

O2
Oxygen molecule 0

MgO
Oxide ion

Na2O
Oxide ion

-2

-2

4. The oxidation number for a simple ion is similar to the charge of the ion. Example : Ion Oxidation number +1 +2 +2 +3 Ion Oxidation number -1 -1 -2 -2

Na

Cl

Cu2+ Fe2+ Fe3+

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5. The oxidation number of the ions from Group 1, 2 and 13 are fixed because the atom of these Groups achieve stable octet electron arrangement by losing 1 e-, 2e- and 3e- respectively. Therefore, the oxidation number for these ions are : Ion from element in Group 1 2 13 Example

Na Mg2+ Al3+

Oxidation number +1 +2 +3

6. The sum of the oxidation numbers for elements in a compound is zero. Example :

KMnO4 +1 x (+1) + x + 4(-2) x

= 0 = +7

-2

7. The sum of the oxidation numbers for elements in a polyatomic ion is equals to the charges of the polyatomic ion. Example :

SO42y -2 y + 4(-2) = -2 y = +6

8. The oxidation number of the Transition Elements and most of non-metal elements are vary from one compound to another. Example : Formula Name Copper(II) oxide Copper(I) oxide Oxidation number +2 +1 Formula Name Iron(II) chloride Iron(III) chloride Oxidation number +2 +3

CuO Cu2O

FeCl2 FeCl3

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Activity 1:State the oxidation number of the underlined element in the following table : Oxidation number (a) (i) (ii) (b) (i) (ii) (iii) Oxidation number (c) (i) (ii) (d) (i) (ii) (iii) (iv)

MnO2 KMnO4 CO32CO2 CO

K2Cr2O7 Na2Cr2O3 NH3 NO2 NH4+ NO3-

Nomenclature of ionic compounds using IUPAC Nomenclature (i) Elements from Group 1, 2 and 13 have only one oxidation number, the names of the compounds are written without the oxidation number. Example :

K2O MgO Al2Cl3

is potassium oxide ; not is magnesium oxide ; not

potassium(I) oxide. magnesium(II) oxide. magnesium(III) chloride.

is aluminium chloride ; not

(ii) Transition elements/metals and most of non metals compounds have more than one oxidation number. The oxidation number of the element is written in Roman numeral, placed in a bracket behind the name of the element. Example : Chemical formula of compound Oxidation number of transition metal/ non metal

Common name Ferrous hydroxide Ferric hydroxide Lead monoxide Lead dioxide Copper oxide Copper oxide
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IUPAC Name Iron(II) hydroxide Iron(III) hydroxide Lead(II) oxide Lead(IV) oxide Copper(II) oxide Copper(I) oxide
Oxidation & Reduction

Fe(OH)2 Fe(OH)3 PbO PbO2 CuO Cu2O 6

+2 +3 +2 +4 +2 +1

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Redox Reaction in terms of change in

The element is a reducing agent.

Oxidation Number

When the oxidation number of an element increases, the element is oxidized.

When the oxidation number of an element decreases, the element is reduced. The element is an oxidizing agent.

A reaction is not a redox reaction

Example :

if no elements undergo a change in oxidation state.

Determine whether the reactions below are redox or not. (a)

AgNO3 +1 +5 -2

NaCl +1 -1

AgCl +1 -1

NaNO3 +1 +5 -2

Oxidation number :

This reaction is not a redox reaction because no changes of oxidation number of all elements in the compounds of substances of reactants and products. (b)

Mg 0

H2SO4 +1 +6 -2

MgSO4 +2 +6 -2

H2 0

Oxidation number :

This reaction is a redox reaction because the oxidation number of magnesium and hydrogen in the substances have changed. Explanation : Magnesium, Mg is oxidized because its oxidation number increases from 0 to +1. Hydrogen ion, H+ is reduced because its oxidation number decreases from +1 to 0. Oxidizing agent is hydrogen ion, H+. Reducing agent is magnesium, Mg. 1.3 Writing Equations For Redox Reactions Equations for redox reactions are : (i) (ii)

Chemical Equation for the reaction. Half equation for oxidation (loss of electron/ increase in oxidation number). Half equation for reduction (gain in electron/ decrease in oxidation number). Overall Ionic equation for redox reaction formed by combining half equation for oxidation and
half equation for reduction (the number of electrons in both the half equations must cancel each other).

(iii)

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Example 1 : Reaction Aluminium and copper(II) sulphate

Chemical Equation for the reaction

2Al + 3CuSO4 Al2(SO4)3

Al
3+ Cu2+ SO42- Al

+ 3Cu
Cu

SO42-

Half equation for oxidation Half equation for reduction

Changing of the coefficient of the half equation of oxidation* Changing of the coefficient of the half equation of reduction* Ionic equation

Al Cu2+ 2Al

Al3+ +

+ 3e

2e Cu

2Al3+ + 6e + 6e 3Cu 2Al3+ + 3Cu

3Cu2+

2Al + 3Cu2+

* Make sure that the number of electrons released in half equation for oxidation are equal to the number of electrons received in half equation for reduction.

Activity 2:1 Sodium metal react with water

sodium

water

Reaction

Sodium and water

Chemical Equation for the reaction

Half equation for oxidation Half equation for reduction

Changing of the coefficient of the half equation of oxidation* Changing of the coefficient of the half equation of reduction* Ionic equation
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Copper(II) oxide react with dry hydrogen gas (Determine the empirical formula of copper(II) oxide)
Copper(II) oxide Dry hydrogen gas

Reaction

Copper(II) oxide and hydrogen gas

Chemical Equation for the reaction

Half equation for oxidation Half equation for reduction

Changing of the coefficient of the half equation of oxidation* Changing of the coefficient of the half equation of reduction* Ionic equation

1.4

Analysing Redox Reactions in : 1.4.1 1.4.2 1.4.3 1.4.4 1.4.5 1.4.6 1.4.7 Displacement of metals from its salt solution. Electrolytic and Chemical Cell (Voltaic cell) Rusting of Iron // Corrosion of Metal Displacement of halogen from its halide solution. Change of : Fe2+ Fe3+ and Fe3+ Fe2+ Transfer of electron at a distance. Reactivity Series of Metals and Its Applications. [Refer to C7 : ELECTROCHEMISTRY]

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1.4.1

Redox Reaction in the Displacement of Metals from its Salt solution Electrochemical Series : Electrochemical Series is an arrangement of elements according to their tendency to release/donate electrons to form a positive ion (cation).

Electrochemical Series

K Na Ca Mg Al Zn Fe Sn Pb H Cu Ag

MORE ELECTROPOSITIVE
Easier to release/donate electrons to form a positive ion (cation)

The higher the position of the metal in the Electrochemical Series, the greater is the tendency of the metal atoms to donate/release electrons (become more Electropositive). Displacement of metals : The metal which is higher in the electrochemical series will donate/lose/release its electrons to the metal ion which is lower in the electrochemical series from its salt solution. The more electropositive metal will be oxidized and dissolves. The less electropositive metal ion will be reduced and deposited.

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Example : A piece of zinc metal plate is dipped in copper(II) sulphate solution. zinc metal + copper(II) sulphate solution
Zn plate

Zn + CuSO4 Zn SO4 + Cu
Zn Zn2+ + 2e
Zinc is more electropositive than copper Zinc corrodes. Copper is less electropositive copper displaced. Observation :

CuSO4(aq)

Cu2+ + 2e

Cu

Zinc plate becomes thinner // Part of zinc plate dissolves Brown solid is formed on the surface of the remaining part of the zinc plate The blue colour of copper(II) sulphate solution becomes colourless

Zn + Cu2+

Zn2+ + Cu

Explanation : In terms of gain/loss of electron Zn is above Cu in the Electrochemical Series. Zinc atom releases/donates/loses two electrons to form zinc ion, Zn2+. Zinc is oxidized. Copper(II) ion, Cu2+ gains/receives two electrons to form copper atom, Cu. Copper(II) ion, Cu2+ is reduced. Zinc has reduced copper(II) ion, Cu2+. Zinc is the reducing agent.

Copper(II) ion, Cu2+ has oxidized zinc. Copper(II) ion is the oxidizing agent. Zn Zn2+ + 2e Cu2+ + 2e Cu Zn + Cu2+ Zn2+ + Cu

Half equation of oxidation : Half equation of reduction : Ionic equation :

In terms of change in oxidation number Zinc is oxidized as its oxidation number increases from 0 to +2. As copper(II) ion, Cu2+ causes Zn to be oxidized, copper(II) ion, Cu2+ is the oxidizing agent. Copper(II) ion, Cu2+ is reduced as its oxidation number decreases from +2 to 0. As zinc , Zn causes copper(II) ion to be reduced, zinc, Zn is the reducing agent.

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1.4.2

Redox Reaction in the Electrolytic and Chemical Cell (Voltaic cell)

Electrolysis : The selected cation will gain/receive electrons and undergoes reduction at the cathode (negatively charged electrode). The selected anion will release/lose its electrons and undergoes oxidation at the anode (positively charged electrode) Chemical cell / Voltaic cell : The metal which is higher in the Electrochemical Series will become the negative terminal and release electrons. The metal undergoes oxidation and dissolves. The metal which is lower in the Electrochemical Series becomes the positive terminal. The ion that is selected for discharge in the solution undergoes reduction and the mass of the positive terminal will increase. The further the distance between two metals in the Electrochemical Series, the higher the voltage of the chemical cell. (a) Differences between an electrolytic cell and a chemical cell : CHARACTERISTIC

ELECTROLYTIC CELL

CHEMICAL CELL

Set up of apparatus

It has cells/ batteries It has Ammeter

It has no cell It has Voltmeter

Same type of electrodes

Different type of electrodes

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Consist of two electrodes (usually carbon / two similar or different metals) connected to batteries and dipped in a electrolyte using connecting wires. Structure Anode : the electrode that is connected to the positive terminal of the battery. Cathode : the electrode that is connected to the negative terminal of the battery.

Consist of two different metals dipped in an electrolyte and connected to a voltmeter / galvanometer / bulb using connecting wires. Negative terminal : the metal that is higher in the Electrochemical Series (more electropositive). Positive terminal : the metal that is lower in the Electrochemical Series (less electropositive ).

Electrical energy to chemical energy

Energy conversion (involves redox reaction)

Chemical energy to electrical energy

(involves redox reaction)

(b) Redox reaction in an electrolytic cell and a chemical cell.

Electrolytic cell
Anode Anion / Metal atom loses its electrons and acts as a reducing agent. e.g :
4OH 2H2O + O2 + 4e Cu Cu2+ + 2e
-

Chemical cell
Cathode Negative terminal (Anode) Positive terminal (Cathode) The metal ion in the electrolyte gains electrons and acts as an oxidizing agent. e.g :
2+

Transfer of electron

Cation in the electrolyte The more gains electrons and acts electropositive metal as an oxidizing agent. loses its electrons and acts as a reducing agent. e.g :
2H + 2e H2 Ag+ + e Ag
+

e.g :
Mg Mg + 2e Zn Zn2+ + 2e

Cu2+ + 2e Cu Ag+ + e Ag

Redox
reaction

Anion / Metal atom undergoes oxidation

Cation undergoes reduction

The more electropositive metal undergoes oxidation

The metal ion in the electrolyte undergoes reduction

Oxidation occurs at the anode in an electrolytic cell and at the negative terminal in a chemical cell.
the term anode is assigned for the electrode at which oxidation occurs, negative terminal anode

Reduction occurs at the cathode in an electrolytic cell and at the positive terminal in a chemical cell.
the term cathode is assigned for the electrode at which reduction occurs, positive terminal cathode

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Activity 3 :1 Diagram below shows the set up of the apparatus used for the electrolysis of potassium sulphate solution.

Carbon electrod X

Carbon electrod Y

potassium sulphate, K2SO4 solution

(a)

State all the ions present in the electrolyte. ...............................................................................................................................................................................

(b)

State the product formed at electrode X and Y. X : ............................................................. Y : ...........................................................................................

(c)

Write the half equation for the reaction at (i) electrode X : ................................................................................................................................................................... (ii) electrode Y : ...................................................................................................................................................................

(d)

Name the substance which is (i) oxidized : ......................................................................................................................................................

(ii) reduced : ......................................................................................................................................................

(e)

Name the (i) oxidizing agent : ...........................................................................................................................................

(ii) reducing agent : ............................................................................................................................................

(f)

State the oxidation number of sulphur in sulphate ion? ...............................................................................................................................................................................

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Table below shows the concentration of sodium chloride in solution X and Y. Solution X 0.001 mol dm-3 Solution Y 2.0 mol dm-3

Both solutions are electrolysed separately using carbon as electrodes. (a) Write the half equation of the reaction that takes place at the anode for electrolysis of : (i) solution X : (ii) solution Y : (b) Name the products formed at the cathode and anode. Product formed at : Anode Solution X Solution Y (c) The products collected at the anode in the electrolysis of solutions X and Y are different. Explain why. .. .. (d) Name the substance oxidized in the electrolysis of : (i) solution X : (ii) solution Y : Cathode

(e)

Name the substance reduced in the electrolysis of : (i) solution X : . (ii) solution Y : .

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The diagram below shows the set up of an apparatus for an experiment.

Magnesium

Copper Copper(II) sulphate solution

Magnesium sulphate solution

Porous pot

(a)

Which electrode is the positive terminal? ...

(b)

Write the observations at the : (i) (ii) negative terminal : ......................................................................................................................... positive terminal : ..........................................................................................................................

(c)

Write the half equation for the reaction that takes place at the : (i) (ii) negative terminal : ......................................................................................................................... positive terminal : ..........................................................................................................................

(d)

Write the ionic equation for the reaction that takes place in the chemical cell above. ...

(e)

Name the substance reduced in the above reaction. ...

(f)

Name the substance that acts as a reducing agent in the above reaction. ...

(f)

How will the voltmeter reading change if the magnesium electrode in the magnesium sulphate solution is replaced by zinc electrode in zinc sulphate solution? Explain why? ... ... ...

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You are provided with the following materials and apparatus. Materials : Zinc plate, copper plate, dilute sulphuric acid, zinc sulphate solution, copper(II) sulphate solution. Apparatus : Beakers, connecting wire, voltmeter, glass tube. (a) By using all the materials and apparatus provided, draw the set up of the apparatus to produce electricity from chemical reactions.

(b) (i) Name the solution that is used as a salt bridge. ... (ii) What is the function of the salt bridge? ... (c) Indicate on the set-up apparatus the following : (i) (ii) (iii) negative terminal positive terminal the direction of electron flow.

(d) Write the half equation for the reaction that occurs at : (i) (ii) negative terminal : . positive terminal :

(e) State the substance that oxidized in the above reaction. ........ (f) Name the substance that acts as an oxidizing agent in the above reaction. ........

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1.4.3

Redox Reaction in Corrosion of Metal [ Rusting of Iron]

Corrosion of metal is a redox reaction in which a metal oxidized to its ion by losing electrons. When metal corrodes, it usually forms a metal oxide coating. Aluminium oxide, for example is non porous and firmly coated the metal. It will protect the aluminium underneath from further corrosion. This further explain the resistance of aluminium to corrosion even though it is higher in the Electrochemical Series ( electropositive metal). Other metals with similar property are zinc, lead, nickel and chromium.

Rusting of iron / corrosion of iron.

Rusting of iron takes place when iron corrodes in the presence of water and oxygen. It is a redox reaction whereby oxygen acts as an oxidizing agent while iron acts as a reducing agent. Mechanism of rusting of iron. O2 Water droplet

O2 B

O2

Iron

The surface of iron at A becomes an anode (negative terminal), the electrode at which oxidation occurs. Iron atom, Fe loses electrons and is oxidized to form iron(II) ion, Fe2+ Half equation of oxidation: Fe Fe2+ + 2e The electrons flow through iron to the edge of the water droplet at B, where the concentration of oxygen here is higher. The iron surface at B becomes cathode( positive terminal) , the electrode at which reduction occurs. Oxygen, O2 gains electrons and is reduced to form hydroxide ions, OH-. Half equation of reduction: O2 + 2H2O + 4e 4OH The iron(II) ion, Fe2+ produced combines with hydroxide ions, OH- to form iron(II) hydroxide.

Fe2+

+ 2OH-

Fe(OH)2

Ionic equation for rusting : 2Fe + O2 + 2H2O 2Fe(OH)2

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Iron(II) ion, Fe2+ is green but rust is brown because iron(II) hydroxide , Fe(OH) 2 undergoes further oxidation by oxygen to form hydrated iron(III) oxide, Fe2O3 . xH2O (rust). [ x is an integer whereby the value varies ] Iron(II) hydroxide , Fe(OH)2 is oxidised by oxygen to form iron(III) hydroxide, Fe(OH)3 Then, iron(III) hydroxide, Fe(OH)3 is decomposed to form hydrated iron(III) oxide (rust). Rust is brittle, porous and not tightly packed. Thus, water and oxygen can penetrate the metal underneath. Iron will undergo continuous corrosion. O2 Fe2O3 . xH2O (rust) Water droplet

Fe2O3 . xH2O (rust) O2

O2

eCathode (positive terminal)

O2 + 2H2O + 4e 4OH
-

eCathode (positive terminal)

O2 + 2H2O + 4e 4OH-

Anode (negative terminal)

Fe Fe2+ + 2e Iron

Rusting of iron occurs faster in the presence of acid or salt because when these substances dissolve in water, the solutions becomes better electrolyte. An electrolyte will increase the electrical conductivity of water. Iron structures at coastal and industrial areas rust faster because of : the presence of salt in the coastal breeze the presence of acidic gases in industrial area such as sulphur dioxide, SO2 and nitrogen dioxide, NO2.

Activity 4 :Draw a labelled diagram to show how the rusting of iron involved the ionization of iron and the flow of electron.

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Controlling Metal Corrosion

(i) Metal corrosion can be controlled by using other metal.

K Na

Ca Mg

Al Zn

Fe Sn

Pb Cu

Ag

Ease of releasing electron increases (more electropositive) When iron is in contact with more electropositive metal for example zinc, rusting of iron is prevented. Zinc, Zn loses electrons more easily than iron, Fe. Zinc corrodes or is oxidized instead of iron. Half equation of oxidation : Zn Zn
2+

+ 2e

The electrons that are released by zinc flow through the iron to the metal surface where there is water and oxygen. Half equation reduction : O2 + 2H2O + 4e 4OH When iron is in contact with less electropositive metal for example copper, rusting of iron is faster. Iron, Fe loses electron more easily than copper, Cu. Hence, iron corrodes / rusts or is oxidized instead of copper. The further apart the metals in the electrochemical series are, the faster the more electropositive metal corrodes. Activity 5 :Diagram below shows the use of zinc plates on an iron ship to prevent rusting.

TAQ 8388

Iron ship Zinc plate Sea water

(a)

Explain how the zinc plates protect the iron ship from rusting.

(b)

Write the half equation for the reaction in (a).

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Activity 6 :1 The diagram shows the set up of the apparatus to study the effect of other metals on the rusting of iron nails.

SPM 2008 Q9 (b)

Jelly + phenolphthalein + potassium hexacyanoferrate(III) solution

Zinc Iron nail

Magnesium Iron nail Iron nail

Copper Iron nail

K Na Ca Mg Al Zn Fe Sn Pb H Cu Ag

(a) What is the function of : (i) phenolphthalein? (ii) potassium hexacyanoferrate(III) solution? (b) State the observation for each test tube P, Q, R and S after a days. (i) Test tube P (ii) Test tube Q (iii) Test tube R (iv) Test tube S

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(c) Based on the observations, (i) state the metals that can prevent the rusting of iron nail (ii) state the metal that can accelerate the rusting of iron nail. (iii) arrange the four metals i.e. iron, zinc, magnesium and copper in ascending order of their electropositivity. (d) (i) State the type of reaction that takes place when iron rusts. (ii) Write the half equation for the reaction in (d) (i). (iii) What is the purpose of test tube R in this experiment?

The diagram below shows three iron nails that are coiled with stannum, metal Y, and metal Z respectively and placed in three different beakers.

Tin

Z B C

Each beaker is filled with aqueous sodium chloride. After a few days the following results are obtained. Beaker A B C Observation The iron nail rusts a little. The iron nail does not rust. The iron nail rusts a lot.

(a) Based on the observations, arrange the metals i.e. tin, Y and Z in a descending order of their electropositivity. .., .,
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(b) Suggest one possible metal for Y : . Z :

(c) Explain why the iron in beaker B does not rust.

(d) For the chemical changes that takes place in beaker A, write the : (i) oxidation half equation : (ii) reduction half equation : (ii) overall ionic equation :

(c)

Metals will corrode when exposed to the atmosphere over a period of time. The rate of corrosion depends on the position of the metal in the Electrochemical Series. If magnesium and iron are exposed to the atmosphere. Which metal will corrode faster? Explain your answer. ............................. .............................

(d)

Why are the products made of aluminium self-protected from corrosion? ............................. .............................

(e)

Electroplating is one way to control the rusting of iron. Suggest two other ways to prevent iron from rusting? .............................

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1.4.4 Redox Reaction In Displacement of Halogen From Its Halide Solution. a) Electronegativity Series of Halogen and Halide HALOGEN HALIDE

Cl2 Electronegativity
of halogens increases. [A measurement of the strength of an atom in its molecule to attract electrons towards its nucleus to form negative ions] Bromine molecule

Chlorine water

ClChloride ion

(Potassium chloride solution)

Br2
Chlorine molecule Bromine water

BrBromide ion

(Potassium bromide solution)

The tendency for a halide to become a halogen increases.

I2
Iodine molecule Iodine water

IIodide ion

Potassium iodide solution)

The more electronegative halogen : can attract electrons from halides that are less electronegative. displaces less electronegative halogen from its halide solution gains electrons and acts as an oxidizing agent. undergoes reduction to form halide ions. Example :

Cl2

2e

2Cl-

Chlorine molecule :

gain / lose two electrons. undergo oxidation / reduction. acts as an oxidizing / reducing agent.

The halide ions of the less electronegative halogen : lose their electrons, undergo oxidation, acts as a reducing agent. Example :

2I- I2
Iodide ion :
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2e

gain / lose electrons undergo oxidation / reduction. acts as a oxidizing / reducing reducing agent. 24
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Activity 7 :1 Predict whether the following reactions occur or not. [ If the reaction occurs, put a tick ( ) ; if no reaction occurs, put a cross ( X ) ] Reactants 1 2 3 4 5 6 7 / X Products

KI KI KBr NaI NaBr KCl NaCl

+ + + + + + +

Cl2 Br2 Cl2 Br2 I2 Br2 I2

A few drops of chlorine water are added to 2 cm3 of potassium iodide solution and the mixture is then shaken thoroughly.

Chlorine water

Potassium iodide solution

Half equation for reduction Half equation for oxidation Ionic equation

: : :

Cl2 + 2e- 2I- I2 Cl2 + 2I-

2Cl-

+ 2e2Cl- + I2

Explanation : Explanation : Chlorine molecules, Cl2 gain / lose electrons to form chloride ions, Cl- . Chlorine molecule is oxidized / reduced. Iodide ions, I- gain / lose to form iodine molecule, I2. Iodide ions are oxidized / reduced. Iodide ions have oxidized / reduced chlorine molecule, Cl2 . Iodide ion is an oxidizing / reducing. Chlorine molecules, Cl2 has oxidized / reduced iodide ions. Chlorine is a oxidizing / reducing.

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Note :
The colour of halogen cannot be differentiated in aqueous solution, especially bromine and iodine. The presence of halogens is confirmed using 1,1,1 trichloroethane, CH3CCl3

aqueous solution layer 1,1,1-trichloroethane layer

Two layers are formed when an aqueous solution of halogen is mixed with 1,1,1-trichloroethane. The denser 1,1,1-trichloroethane will be at the bottom and less dense aqueous solution will be at the top.

Halogen Chlorine, Cl2 Bromine, Br2 Iodine, I2

Colour in aqueous solution Pale yellow or colourless Brown / yellowish brown / yellow (depends on concentration) Brown / yellowish brown / yellow (depends on concentration)

Colour in 1,1,1 trichloroethane, CH3CCl3

Pale yellow or colourless Brown / yellowish brown / yellow

(depends on concentration)

Purple

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Activity 8 :Iodine is formed when bromine water is added to potassium iodide solution.

(a) How do you confirm the formation of iodine in the experiment? (b) Write the half equation for the chemical change that takes place in : (i) (ii) (iii) (iv) bromine water :

potassium iodide : a reducing agent : an oxidizing agent :

(c) Write ionic equation for redox reaction. (d) Suggest halogen X that can replace bromine water so that iodine is also formed.

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1.4.5 Redox Reaction In The Change Of

Fe 2+ Fe 3+ and Fe 3+ Fe 2+

(a) Changing of iron(II) ion, Fe2+ to iron(III) ion, Fe3+

Bromine water

Iron(II) sulphate solution

Heat

Iron (II) ion, Fe

2+

undergoes oxidation by losing its electron to form iron(III) ion, Fe

3+

Oxidation half equation :

Fe2+

Fe3+ + e

The substance added is an oxidizing agent such as bromine water, Br2. Bromine molecule gains electrons and undergoes reduction to form bromide ion, Br-. Reduction half equation :

Br2 + 2e 2Br-

Observation for the change of iron(II) ion, Fe2+ to iron(III) ion, Fe3+ :
(i) (ii) Iron(II) solution changes colour from pale green to yellow

Brown colour of bromine water decolourises

3+

Confirmatory test for iron(III) ion, Fe

Add sodium hydroxide solution to the solution until excess. A brown precipitate is formed. It is insoluble in excess sodium hydroxide solution. Other oxidizing agents that can replace bromine water to change Fe2+ to Fe3+ are : Oxidizing agent Chlorine water, Cl2 Acidified potassium manganate(VII) solution, KMnO4 Acidified potassium dichromate(VI) solution, K2Cr2O7 Hydrogen peroxide, H2O2 Reduction half equation

Cl2 + 2e 2ClMnO4+ 8H+ + 5e Mn2+ + 4H2O

Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O H2O2 + 2H+ + 2e 2H2O

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Activity 9 :1 Chlorine water is added drop by drop to 2 cm3 of iron(II) sulphate solution in a test tube. The test tube is warmed gently. (a) Write the : Half equation of oxidation : .. Half equation of reduction : .. Overall ionic equation :

Diagram 2 shows the set- up of apparatus to investigate the reaction between iron(II) chloride solution and potassium manganate(VII) solution through the transfer of electrons at a distance.

Carbon electrode P

Carbon electrode Q

Iron(II) chloride solution

Potassium mangganate(VII)

Dilute sulphuric acid DIAGRAM 2

(a) What is the function of dilute sulphuric acid? (b) In Diagram 2, draw the direction of the flow of electrons. (c) (i) What is the colour change in the solution around electrode P? .................................................................................................................................. (ii) Describe a chemical test to determine the product formed in the solution at electrode P. .............. ...............
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(d) What is the substance that is being oxidized in the experiment? Explain why. ..... ..... (e) Write the half equation for the reaction that occurs at electrode Q. ..... (f) Suggest another reagent that can replace potassium manganate(VII) solution. .................... (g) What is the change in oxidation number of manganese in the reaction? ......

(b) Changing of iron(III) ion, Fe3+ to iron(II) ion, Fe2+

Iron(III) sulphate solution Zinc powder Heat

Iron (III) ion, Fe3+ undergoes reduction by gaining one electron to form iron(III) ion, Fe2+ Oxidation half equation :

Fe3+ + e Fe2+

The substance added is an reducing agent such as zinc, Zn. Zinc atom loses electrons and undergoes oxidation to form zinc ion, Zn2+. Reduction half equation :

Zn Zn2+ + 2e 3Zn + 2Fe3+ 3Zn2+ + 2Fe

Ionic equation

Observation for the change of iron(III) ion, Fe3+ to iron(II) ion, Fe2+ :
(i) (ii) Iron(III) solution changes colour from brown to pale green Some zinc powder dissolved

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Confirmatory test for iron(II) ion, Fe2+ : Add sodium hydroxide solution to the solution until excess. A green precipitate is formed. It is insoluble in excess sodium hydroxide solution. Other reducing agents that can replace zinc to change Fe2+ to Fe3+ are : Reducing agent Magnesium, Mg Sulphur dioxide, SO2 Hydrogen sulphide, H2S Sodium sulphite solution, Na2SO3 Half equation of Oxidation

Mg Mg2+ + 2e SO2 + 2H2O SO42- + 4H+ + 2e H2S 2H+ + S + 2e SO32- + H2O SO42- + 2H+ + 2e

Activity 10 :1 The following is an equation represents a redox reaction.

2Fe3+(aq)

H2S(g)

2Fe2+(aq)

2H+ (aq) + S(s)

Based on the redox reaction : (a) Write half equation for : (i) oxidation : (ii) reduction :

H2S 2H+ + S + 2e // S2- S + 2e Fe3+ Fe2+ + e

(b) Name the substance that acts as : (i) Oxidizing agent : Iron(III) ion, Fe3+ (ii) Reducing agent : Hydrogen sulphide, H2S // sulphide ion, S (c) Change in oxidation ; (i) Oxidation number of iron is decrease from +3 to +2 (ii) Oxidation number of sulphur is increase from -2 to 0
2-

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1.3.6 Redox Reaction In term of Transfer of Electron at a Distance 1. Transfer of electron at a distance occurs when two solutions of reducing agent and oxidizing agent are separated by an electrolyte in a U-tube. 2. Redox reaction occurs as a result of electron flow through an external circuit. 3. Electrons flow from the reducing agent (loses electrons) to the oxidizing agent (gains electrons) through the connecting wires and can be detected by a galvanometer. 4. Carbon electrode that is immersed in a reducing agent is known as the negative terminal (anode). 5. Carbon electrode that is immersed in an oxidizing agent is known as the positive terminal (cathode). 6. The electrolyte allows the movement of ions and completes the electric circuit. 7. The diagram shows the set up of the apparatus for the electron transfer at a distance.

Carbon electrode

+
Carbon electrode

Reducing agent Loses electron Undergoes oxidation

Oxidizing agent Gains electron Undergoes reduction electrolyte

8. Reducing agent loses its electron and undergoes oxidation. 9. Oxidation agent gains its electron and undergoes reduction.

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Examples of common substances used as reducing agents are : Substance Potassium iodide, KI Potassium bromide, KBr Iron(II) chloride // Iron(II) sulphate In U-tube cell / a chemical cell electrode that is immersed in the reducing agent becomes the negative terminal or anode because the agent loses electrons and undergoes oxidation. Oxidation agent gains the electrons and undergoes reduction. Half equation for oxidation Observation/ Test

Examples of common substances used as oxidizing agents are :

Substance Acidified potassium manganate(VII) Acidified potassium/ sodium dichromate(VI) Chlorine water Bromine water Iron(III) chloride, Iron(III) sulphate Half equation for reduction Observation // Confirmatory test

MnO4-

+ 8H+ + 5e Mn2+ + 4H2O

Cr2O72- + 14H+ + 6e 2Cr3+ + 7H2O Cl2 + 2e 2ClBr2 + 2e 2BrFe3+ + e Fe2+

In a chemical cell / U-tube cell electrode that is immersed in an aqueous solution of an oxidizing agent becomes the positive terminal or anode because the agent gains electrons and undergoes reduction.

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Complete the table below for the electron transfer at a distance Half equation for Oxidizing Reducing oxidation : Reactants losses of electron agent agent negative terminal

Half equation for reduction : gains of electron positive terminal

Ionic equation

Diagram for the set up of apparatus : The direction of electron flow Positive / negative terminal

FeSO4(aq)
and

Br2(aq)

KI(aq)
and

KMnO4(aq)

FeSO4(aq)
and

K2Cr2O7(aq)

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1.3.7 Redox Reaction In The Reactivity Series Of Metals And Its Applications (a) Reactivity series of metals is an arrangement of metals in accordance to the reactivity of their reactions with oxygen to form metal oxides.

Reactivity of metal towards oxygen increases.

K Na Ca Mg Al C Zn H Fe Sn Pb Cu

The more reactive metal is able to remove oxygen from less reactive metal oxide. The more reactive metal gains oxygen to form metal oxide and undergoes oxidation / oxidation number of metal increases. The less reactive metal oxide loses oxygen to form metal and undergoes reduction / oxidation number of metal in the metal oxide decreases. The more reactive metal has reduced the less reactive metal oxide and acts as reducing a agent. The less reactive metal cannot remove oxygen from more reactive metal oxide.

The empirical formula of metal oxide for a more reactive metal than hydrogen in the reactivity series (such as magnesium) can be determined by heating the metal strongly in a crucible. The empirical formula of metal oxide for a less reactive metal than hydrogen (such as copper) can be determined by passing dry hydrogen gas through strongly heated metal oxides in a combustion tube.

(b) The metals are arranged in the Reactivity Series by observing how vigorously they react with

oxygen. The metal at the top of the series burns most vigorously and most quickly in oxygen.
(c) Carbon reacts with oxygen to form carbon dioxide. Carbon is also an element in the Reactivity Series of metals. (d) Determination the position of Carbon in Reactivity Series of metals : (i) If carbon can remove oxygen from a metal oxide // (reduce the metal oxide to metal),

Carbon + metal oxide metal + carbon dioxide

Carbon is above the metal in the Reactivity Series of metal.

(ii) Conversely, if carbon cannot remove oxygen from metal oxide, carbon is less reactive than the metal in the reactivity series of metal. Thus, no reaction will occur.

Carbon + metal oxide

(no reaction)

Carbon is below the metal in the Reactivity Series of metal.

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(e) Determination the position of Hydrogen in Reactivity Series of metals : (i) If hydrogen can remove oxygen from a metal oxide // (reduce the metal oxide to metal),

Hydrogen + metal oxide metal + water

Carbon is above the metal in the Reactivity Series of metal.

(ii) If hydrogen is unable to remove oxygen from metal oxide, hydrogen is less reactive than the matel in the Reactivity Series of metals.

Note :
If metal X is more reactive than metal Y, then metal X can remove oxygen from the oxide of metal Y. metal X can reduce oxide of metal Y.

X + Y oxide

X oxide + Y

X oxide + Y (no reaction)

(f) Application of the Reactivity Series Metals that are located below carbon in the Reactivity Series (less reactive than carbon) can be extracted from their ores (metal oxides) using carbon. Metal oxide + Carbon Metal + Carbon dioxide Carbon is released as carbon dioxide gas after the reaction (i) Carbon is widely used to extract iron (Fe), tin/stanum (Sn), zinc (Zn) and lead (Pb) from their ores. Carbon is more reactive than these metals and act as reducing agent in the metal extraction process. The extraction is carried out in the a blast furnace. Hot air is pumped to the blast furnace to burn carbon and carbon monoxide is produced . In the blast furnace, a series of chemical reactions take place. The extraction of iron, Fe :

(ii)

C(s) + O2 (g) CO2(g) C(s) + CO2(g) 2CO (g)

Both carbon, C and carbon monoxide, CO can remove oxygen from the ores

2Fe2O3(s) + C(s)

4Fe(s)

+ 3CO2(g)

Fe2O3(s) + CO(g) 2Fe(s) + 3CO2(g)

Iron , Fe is extracted from its ore, hematite ( Fe2O3)

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The extraction of Tin, Sn :

SnO2(s) SnO2(s)

+ C(s)

Sn(s)

+ CO2(g) + 2CO2(g)
Tin, Sn is extracted from its ore, cassiterite (SnO2).

+ 2CO(g) Sn(s)

Metals that are located above carbon in the Reactivity Series (more reactive than carbon) can be extracted from their ores (metal oxides) by electrolysis of molten ores using carbon electrode. Extraction of aluminium metal, Al from aluminium oxide, Al2O3 (bauksite) [ Refer to Chapter 6/Form 4 : Electrochemistry ] The empirical formula of metal oxide : for a more reactive metal than hydrogen in the Reactivity series (such as magnesium) can be determined by heating the metal strongly in a crucible. for a less reactive metal than hydrogen (such as copper) can be determined by passing hydrogen gas through strongly heated metal oxides in a combustion tube. [ Refer to Chapter 3/Form 4 : Chemical Formulae & Equations ]

Activity 11 :1 Determine whether the following reactions occur or not. If the reaction occurs, mark and if not, mark X. Reactants (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) Hydrogen + zinc oxide Magnesium oxide + carbon Copper + zinc oxide Aluminium + carbon dioxide Carbon + silver oxide Hydrogen oxide + copper Iron(II) oxide + hydrogen gas Magnesium + steam carbon dioxide + lead Iron + lead(II) oxide / X Chemical Equation

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Diagram below shows the set up of apparatus to investigate the reactivity of metal P, Q and R towards oxygen. Metal P, Q and R is heated before hydrogen peroxide is poured into the conical flask.

Heat

Hydrogen peroxide + Manganese(IV) oxide

The observations are given below Metal P Q R Observation Burns fairly bright. The residue is yellow when hot but turns white when cold. Glows faintly. The residue is black. Burns vigorously with bright flame. The residue is white.

(a) Write chemical equation for the decomposition of hydrogen peroxide. .. (b) What is the function of manganese(IV) oxide in the experiment? .. (c) Based on the observations, arrange the metals P, Q and R in a ascending order of their reactivity. .. (d) Name the P and Q. Metal P :. Metal Q : (e) Chemical formula the oxide of metal R is R2O3. This oxide can be reduced by hydrogen gas to for metal R. (i) Write an equation for the reaction between R2O3 with hydrogen. (ii) Name the oxidation agent in this reaction.
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(iii)

Draw a labeled diagram of the apparatus that can used to conduct this experiment.

(f) (i)

Name another substance that can replace hydrogen peroxide.

(ii) Write an equation to represent the reaction that occurs in (f) (i).

Activity 12 :REVISION : 1. REDOX REACTION is a reaction where oxidation and .occur at the time. 2. Oxidation involved : losses of .. gains of.... .of electrons. . oxidation number.

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3. Reduction involved : losses of .. gains of.... . of electrons. . oxidation number.

4.

Mg

Mg2+ + 2e

Magnesium atom is oxidized because : magnesium atom is released .. electrons. the oxidation number of magnesium is . from .. to .. 5.

H2S + Cl2

S + 2HCl

Hydrogen sulphide, H2S is oxidized to . H2S acts as an . agent. Chlorine gas,Cl2 is reduced to . Cl2 undergoes reduction and acts as an . agent. 6. (a)

Zn + 2HCl

ZnCl2 + H2

Zn Zn2+ + 2e

Zinc atom undergoes because its .. electrons. Its oxidation number increases from to Zinc acts as an ..agent (b) 2H+ + 2e H2 Hydrogen ion undergoes because it .. electrons. Its oxidation number from to Hydrogen ion acts as an ..agent. 7.

Cu2+ + 2e

Cu

Copper(II) ion, Cu2+ undergoes . Cu2+ ion ... electrons. Its oxidation number decreases from .to Cu2+ ion acts as an.agent.

END OF CHAPTER 12

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