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CHAPTER 3

Oxidation and Reduction

(A) Redox Reactions, RR


After this lesson, you should be able to: State what oxidation is State what reduction is Explain what redox reaction is State what oxidizing agent is State what reducing agent is Calculate the oxidation number of an element in a compound Relate the oxidation number of an element to the name of its compound using the IUPAC nomenclature Explain with examples oxidation and reduction processes in terms of the change in oxidation number Explain with examples oxidation and reduction processes in terms of electron transfer Explain with examples oxidizing agents and reducing agents in redox reactions Write oxidation and reduction half-equations and ionic equations.

What is Redox Reaction? Redox reaction are chemical reactions involving oxidation and reduction occurring simultaneously.

Explanation of Redox Reaction, RR


Redox reactions can be explained in term of: Loss or gain of oxygen Loss or gain of hydrogen Transfer of electrons Changes in oxidation number
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Explanation of RR based on

Loss or Gain of Oxygen


Oxidation is a chemical reaction in which oxygen is added to a substance Reduction is defined as the loss of oxygen from a substance The substance that causes oxidation is called oxidizing agent (oxidant) The substance that causes reduction is called the reducing agent (reductant)
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Example 1:
2CuO(s) CO2(g) + C(s)

Gains oxygen (oxidation)

2Cu(s)

Loses oxygen (reduction)

CuO is reduced to Cu C is oxidized to CO2 CuO acts as oxidizing agent (oxidant) C acts as reducing agent (reductant)
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Explanation of RR based on

Loss or Gain of Hydrogen


Oxidation is the loss of hydrogen from a substance Reduction is the gain of hydrogen from a substance

Example 2:
H2S(g) + Cl2 (g)
Loses hydrogen (oxidation)

Gains hydrogen (reduction)

S(s)

2HCl(g)

H2S is oxidized to S Cl2 is reduced to HCl Cl2 acts as oxidizing agent (oxidant) H2S acts as reducing agent (reductant)
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Practice A1:
Study the following equations and identify the oxidized substances, reduced substances, oxidant and reductant. a)2HBr(aq) + Cl2(l) 2HCl(aq) + Br2(l) b)Mg(s) + PbO(s) MgO(s) + Pb(s) c)CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) d)Fe3O4(s) + 4CO(g) 3Fe(s) + 4CO2(g) e)PbS(s) + 4H2O2(aq) PbSO4(s) + 4H2O(l)
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Explanation of RR based on

Transfer of Electrons
Oxidation is the loss of electrons Reduction is the gain of electrons Oxidizing Agent is electron acceptors Reducing Agent is electron donors

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Example 3:
Zn(s) + Cu2+ (s)
Loses electron (oxidation)

Gains electron (reduction)

Zn2+ (aq)

+ Cu(s)

Loss eGain e-

Zn(s) Cu2+ (aq) + 2e-

Zn2+ (aq) + 2eCu(s)

------------------------------------------------------------Zn(s) + Cu2+ (s) + 2e- Zn2+ (aq) + Cu(s) + 2e---------------------------------------------------------------------Ionic Eq. Zn(s) + Cu2+ (s) Zn2+ (aq) + Cu(s) ========================================= 11

Practice A2:
Study the following redox reactions a) Cu(s) + 2Ag+(aq) Cu2+ (aq) + 2Ag(s) b) Cl2(g) + 2Br(aq) 2Cl(aq) + Br2(l) c) Ca(s) + 2HCl(aq) CaCl2(aq) + H2(g) d) 2Na(s) + Cl2(g) 2NaCl(s) e) 2Fe2+(aq) + Br2(aq) 2Fe3+(aq) + 2Br(aq) For each of the above reaction above, i) Write the half equations ii) Identify the
Oxidized substance Reduced substance Oxidizing agent Reducing agent based on the transfer of electrons

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What is an Oxidation Number?


The oxidation number or oxidation state of an element is the charge that the atom of the element would have if complete transfer of electron occurs.

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Rules in assigning Oxidation Number


Rule 1: The oxidation number of an atom in its elemental state is zero. For example: The oxidation number of each atom in Mg, Cu, Na, H2, O2, Cl2 and P4 is zero.
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Rules in assigning Oxidation Number


Rule 2: The oxidation number of monoatomic ion is equal to its charge For example:
Ion Oxidation Number Na+ +1 Mg2+ +2 Al3+ +3 Br 1 S2 2 N3 3

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Rules in assigning Oxidation Number


Rule 3: The oxidation number of hydrogen in a compound is always +1 except in metal hydrides, where it is 1. For example: The oxidation number of H in H2O and NH3 is +1. However, the oxidation number of H in sodium hydride, NaH is 1
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Rules in assigning Oxidation Number


Rule 4: The oxidation number of oxygen in a compound is always except in peroxides. 2 For example: The oxidation number of O in H2O and MgO is . However, the oxidation number of O in 2 hydrogen peroxide, H2O2 is 1
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Rules in assigning Oxidation Number


Rule 5: The oxidation number of fluorine in all its compound is 1. The oxidation number of other halogens (Cl, Br, I) in their compounds is except 1 when they combine with more electronegative elements such as oxygen or nitrogen.
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Rules in assigning Oxidation Number


Rule 6: The sum of the oxidation numbers of all the elements in the formula of a compound must be zero. The sum of the oxidation numbers of all the elements in the formula of a polyatomic ion must be equal to the charge of the ion.
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Calculation of Oxidation Number, ON


Example 1: Determine the oxidation number of nitrogen in NH3. NH3 x +1

Assume that the oxidation number of nitrogen is X The ON of H in NH3 is +1 (rule 3) The sum of ON of all atoms = 0 (rule 6) Thus , x + 3(+1) = 0 x+3=0 x= 3

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Calculation of Oxidation Number, ON


Example 2: Determine the oxidation number of copper in Cu2O

Cu2O x 2

Assume that the oxidation number of copper is X The ON of O in Cu2O is (rule 4) 2 The sum of ON of all atoms = 0 (rule 6) Thus , 2x + ( = 0 2) 2x = 0 2 x = +1

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Calculation of Oxidation Number, ON


Example 3: Determine the oxidation number of sulphur in SO42

SO4 2 x 2

Assume that the oxidation number of sulphur is X The ON of O in SO42 is (rule 4) 2 The sum of ON of all atoms = (rule 6) 2 Thus , x + 4( = 2) 2 x = 8 2 x = +6

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Calculation of Oxidation Number, ON


Example 4: Determine the oxidation number of manganese in MnO4 MnO4 x 2

Assume that the oxidation number of manganese is X The ON of O in MnO4 is (rule 4) 2 The sum of ON of all atoms = (rule 6) 1 Thus , x + 4( = 2) 1 x = 8 1 x = +7

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Practice A3:
Determine the oxidation number of the underlined elements in the following compound a) CO2 b)MgF2 c) H3PO4 d) V2O5 e) CO i) N2O f) NH4+ j) H2O2 g) SO3 k) S2O32 o) BrO3 w) HClO2 h) ClO4l) CrO42 p)VO2 x)ClO2
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m) Cr2O72 n) Al2O3 u) HCl v) HClO

q) PbO22 r) NO3 s) NO2 y) HClO3 z)HClO4

t) CO32

Oxidation Number and IUPAC Nomenclature


Formula of Compound Oxidation Number of Underlined Metal IUPAC name

FeCl2 FeCl3 CuCl CuSO4 Mn(NO3)2 MnO2 K4Fe(CN)6 K3Fe(CN)6

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

Iron(II) chloride Iron(III) chloride Copper(I) chloride Copper(II) sulphate Manganese(II) nitrate Manganese(IV) oxide Potassium hexacyanoferrate (II) Potassium hexacyanoferrate (III) 25

Common Names and IUPAC Names for some compound


Molecular Formula ON of metalCommon Name IUPAC name

Na2SO3 Na2SO4 NaNO2 NaNO3 HNO2 HNO3 H2SO4

+4 +6 +3 +5 +3 +5 +6

Sodium sulphite Sodium sulphate Sodium nitrite Sodium nitrate Nitrous acid Nitric acid Sulphuric acid

Sodium sulphate(IV) Sodium sulphate(VI) Sodium nitrate(III) Sodium nitrate(V) Nitric(III) acid Nitric (V) acid Sulphuric (VI) acid
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Explanation of RR based on The Changes in Oxidation Number


An increase in oxidation number indicates Oxidation A decrease in oxidation number indicates Reduction

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Example 4:
2Mg(s)
Oxidation Number 0

Decrease in oxidation number

O2 (s)
0

2MgO(s)
+2 2

Increase in oxidation number

+2

Mg2+

Increase in Oxidation Number (Oxidation)

decrease in Oxidation Number (Reduction)

O2

Mg

O2-

-2

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Explanation
The oxidation number of Magnesium increases from 0 to +2. Magnesium undergoes oxidation to magnesium ion The oxidation number of Oxygen decrease from 0 to 2 Oxygen undergoes reduction to oxide ion Magnesium acts as reducing agent Oxygen acts as oxidizing agent
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Practice A4
a) b) c) d) 2H2 + O2 2H2O 2Na + Br2 2NaBr Pb + 2Ag+ Pb2+ + 2Ag Zn + 2HCl ZnCl2 + H2

Explain the above redox reactions based on the changes in oxidation number. Your explanation should includes: i) oxidized and reduced substance in each reaction. Give reason for your answer. ii) oxidizing agent and reducing agent in each 30 reaction. State what happens to them

Summary on the Definition of Oxidation and Reduction Oxidation


Gain of Oxygen Loss of Hydrogen Loss of Electrons Increase in Oxidation Number

Reduction
Loss of Oxygen Gain of Hydrogen Gain of Electron Decrease in Oxidation Number
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Examples of Redox Reaction


1. 2. 3. 4. 5. 6. 7. 8. Combustion Extraction of Metals Corrosion of Metals Electrochemistry ( Reaction happen in Electrolytic Cell and Voltaic Cell) Change of Fe2+ to Fe3+ and vice versa Displacement of Metal from its salt solution Displacement of halogen from its halide solution Transfer of electrons at a distance
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Examples of Non Redox Reaction


Neutralization Precipitation Reaction

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Change of Fe2+ to Fe3+ & vice versa


Iron metal (Fe) exhibits two oxidation numbers, i.e. +2 and +3 Fe2+ ion can be easily converted into Fe3+ ion. Fe3+ ion can also be easily converted into Fe2+ ion.
Loss of electron

Fe

2+

oxidation

Fe3+

Gain of electron reduction


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Oxidation of Fe2+ to Fe3+


Procedure: 1. Pour 2cm3 of freshly prepared iron(II) sulphate, FeSO4 solution into a test tube. 2. Using a dropper, add bromine water drop by drop until no further changes are observed. 3. Warm the test tube gently 4. Add NaOH solution slowly into the test tube until it excess. 5. Record the observation.
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Oxidation of Fe to Fe
2+
Solution Used Observations

3+

FeSO4 + Br2

Reddish brown bromine water was decolourized. Green FeSO4 solution turn brown. When NaOH solution was added, a brown precipitate formed. The precipitate is insoluble in excess NaOH

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Oxidation of Fe2+ to Fe3+


Half Equation:

Oxidation: Reduction

Fe2+ (aq) Fe3+(aq) + e: Br2(aq) + 2e- 2Br(aq)

------------------------------------------------------------------------------------

Ionic Equation :

2Fe2+ (aq) + Br2 (aq) 2Fe3+(aq) + 2Br (aq)


===========================================================

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Reduction of Fe3+ to Fe2+


Procedure: 1. Pour 2cm3 of iron(III) sulphate, Fe2(SO4)3 solution into a test tube. 2. Add half a spatula of zinc powder to the solution. Shake the mixture until no further changes are observed. 3. Filter the mixture. 4. Add NaOH solution slowly into the filtrate until in excess. 5. Record the observation.
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Reduction of Fe3+ to Fe2+


Solution Used Observations

Fe2(SO4)3 + Zn

Part of Zn powder dissolved. Brown Fe2(SO4)3 solution turn green. When NaOH solution was added to the filtrate, a green precipitate was formed. The precipitate is insoluble in water.

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Reduction of Fe3+ to Fe2+


Half Equation: Oxidation : Zn(s) Zn2+ (aq) + 2eReduction : Fe3+ (aq) + e- Fe2+(aq) -------------------------------------------------------------------------Ionic Equation : Zn(s) + 2Fe3+ (aq) Zn2+ (aq) + 2Fe2+(aq) ============================================
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Displacement of Metals
A metal displacement reaction involves a metal and the salt solution of another metal. Displacement Reaction took place if any of these observation is obtained:
a deposition of solid occurs at the bottom of the test tube. a change in colour of the salt solution a decrease in the amount or size of the metal used Test tube becomes hotter
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Displacement of Metals
A more electropositive metal can displace a less electropositive metal from its aqueous salt solution. A less electropositive metal cannot displace a more electropositive metal from its aqueous salt solution

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Displacement of Metals
K Na Ca Mg Al Zn Fe Sn Pb Cu Hg Ag Less electropositive More electropositive

A more electropositive metal is located at higher position in the electrochemical series, ES. A less electropositive metal is located at lower position in the electrochemical series, ES.
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Examples:

Displacement of Metals

Fe(s) + CuSO4(aq) Cu(s) + FeSO4(aq) Cu(s) + 2AgNO3(aq) 2Ag(s) + Cu(NO3)2(aq) Mg(s) + FeSO4(aq) Fe(s) + MgSO4(aq) Cu(s) + FeSO4(aq) No reaction Zn(s) + MgSO4(aq) No reaction
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Displacement of Metals

Zinc displaces copper metal from copper(II) sulphate solution Zn(s) + CuSO4(aq) Cu(s) + ZnSO4(aq) Half Equation: Zn(s) Zn2+(aq) + 2e- (Oxidation) Cu2+(aq) + 2e- Cu(s) (Reduction) Overall ionic equation: Zn(s) + Cu2+(aq) Cu(s) + Zn2+ (aq)
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Displacement of Metals
Observation: (a) Brown copper metal deposited (b) The colour of the solution changes from blue to colourless. (c) The temperature of the mixture increases. ( all displacement reaction are exothermic)

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Displacement of Halogen
A more reactive halogen can displace a less reactive halogen from its aqueous halide salt solution. A less reactive halogen cannot displace a more reactive halogen from its aqueous halide salt solution. Cl,
More reactive

Br,

I
Less reactive

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Colour of halogen
Halogen Chlorine Bromine Iodine Colour in aqueous Colour in solution 1,1,1-trichlorethane Pale yellow Brown Brown Colourless Brown Purple

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Displacement of halogen

Procedure: 1. 1cm3 of aqueous potassium iodide solution, 1cm3 of bromine water and 1cm3 of 1,1,1-trichloroethane are added into a test tube, labelled A. The mixture is shaken. 2. Step 1 is repeated by adding 1cm3 of aqueous potassium bromide solution, 1cm3 of chlorine water and 1cm3 of 1,1,1trichloroethane are added into a test tube, labelled B. The mixture is shaken.
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Displacement of halogen
Result: Test tube Colour of CH3CCl3 Purple Inference

Iodine displaced

Brown

Bromine displaced

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Discussion
Test Tube A Cl2(aq) + 2KBr(aq) Br2(aq) + 2KCl(aq) Cl2(aq) + 2Br (aq) Br2(aq) + 2Cl (aq)
ON : 0 1 0 1

Bromine, Br2 dissolves in CH3CCl3 to give a brown colour Chlorine, Cl2 is reduced. Reducing agent are the Brions. Bromide ions are oxidized. Oxidizing agent is Cl2.

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Discussion
Test Tube B Br2(aq) + 2KI(aq) I2(aq) + 2KBr(aq) Br2(aq) + 2I (aq) I2(aq) + 2Br (aq)
ON : 0 1 0 1

Iodine, I2 dissolves in CH3CCl3 to give a purple colour Bromine, Br2 is reduced. Reducing agent are the Iions. Iodide ions are oxidized. Oxidizing agent is Br2.

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Transfer of Electron at a Distance I

Dilute sulphuric acid

At electrode X Iodide ions lose electron and are oxidized to brown iodine. 2I(aq) I2(aq) + 2eON: -1 0 (oxidation)
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The colour of the solution changes from colourless to brown. The e- released by the iodide ion flow from electrode X to electrode Y along the connecting wires. At electrode Y The bromine molecules surrounding the electrode Y accept the e- and are reduced to bromide ions. Br2(aq) + 2e- 2Br(aq) ON: 0 -1 (Reduction) The colour of the solution changes from brown to colourless. Overall ionic equation: Br2(aq) + 2I(aq) 2Br(aq) + I2(aq) oxidant reductant
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Transfer of Electron at a Distance II

Dilute sulphuric acid

At electrode X Each Iron(II) ion loses an electron and is oxidized to brown iron(III) ion. Fe2+ (aq) Fe3+ (aq) + e ON: +2 +3 (oxidation)
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The colour of the solution changes from green to brown. The e- released by the iron(II) ion flow from electrode X to electrode Y along the connecting wires. At electrode Y The bromine molecules surrounding the electrode Y accept the e- and are reduced to bromide ions. Br2(aq) + 2e- 2Br(aq) ON: 0 -1 (Reduction) The colour of the solution changes from brown to colourless. Overall ionic equation: Br2(aq) + Fe2+ (aq) 2Br(aq) + Fe3+ (aq) oxidant reductant
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Transfer of Electron at a Distance III


X Y

At electrode X Each Iron(II) ion loses an electron and is oxidized to brown iron(III) ion. Fe2+ (aq) Fe3+ (aq) + e ON: +2 +3 (oxidation)
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The colour of the solution changes from green to yellow/ brown. The e- released by the iron(II) ion flow from electrode X to electrode Y along the connecting wires. At electrode Y The manganate(VII) ion, MnO4 gathered at the electrode Y accept the e- and are reduced to manganese(II) ion, Mn2+. MnO4 (aq) + 8H+ (aq) + 5e- Mn2+ (aq) + 4H2O(l) ON: +7 +2 (Reduction)

The colour of the solution changes from purple to colourless.


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Overall ionic equation:


anode cathode

5[Fe2+ (aq) Fe3+ (aq) + e-] MnO4 (aq) + 8H+ (aq) + 5e- Mn2+ (aq) + 4H2O(l)

5Fe2+ (aq) + MnO4 (aq) + 8H+ (aq) 5Fe3+ (aq)+ Mn2+ (aq) + 4H2O(l)

Substance oxidized Substance reduced Oxidizing agent Reducing agent

: : : :

iron(II) ion, Fe2+ manganese(VII) ion, MnO4 manganese(VII) ion, MnO4 iron(II) ion, Fe2+
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Practice A5
A
K2Cr2O7 (aq) + H2SO4(aq) H2SO4(aq) FeSO4(aq)

The figure above shows an experiment on the transfer of electron at a distance a) Identify the i) oxidizing agent ii) reducing agent iii) positive electrode iv) negative electrode b) Explain the changes at the i) negative electrode ii) positive electrode
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