Redox Reactions

1
Division of volumetric (titrimetric) analysis
methods

1) Neutralization analysis
2) Precipitation methods
3) Complexometric titrations
4) Oxidation -reduction methods (REDOX)

2
 Oxidation -reduction methods (REDOX):

 An important class of titrations is reduction

oxidation or “redox” titrations, in which an
oxidizing agent & a reducing agent react

3
 Oxidation -reduction methods (REDOX):

 Involve simultaneous oxidation-reduction

reactions. Involves transfer of electron from one
species to another.
 It includes all the methods where the reacting
substance is oxidized or reduced by the standard
solution.
 Eg Iron II can be analysed by oxidation with a
known volume of standardised permanganate
solution

4
Redox Reactions

 Oxidation is the loss of electrons to an

oxidizing agent (which itself gets reduced)
to give a higher or more positive oxidation
state,..
 … & reduction is the gain of electrons from
a reducing agent (which itself gets
oxidized) to give a lower or more
negative oxidation state.

5
 ELECTROCHEMICAL CELLS & ELECTRODE
POTENTIALS

Oxidation is a loss of electrons.

Reduction is a gain of electrons.

“OIL RIG” is a good mnemonic to help remember

this.

6
 GCSE
Oxidation: Reduction:
•Gain of oxygen •Loss of oxygen
•Loss of electrons •Gain of electrons

Increase in Decrease in
oxidation oxidation
number number
 4 Experiments:
1. Burning magnesium
2. Copper in silver nitrate solution
3. Chlorine solution and potassium
iodide solution
4. Exploding hydrogen

• Word equation
•Balanced symbol equation
 Oxidised –
gains oxygen

2Mg(s) + O2(g)  2MgO(s)

Must be a redox!

Oxidised – loss of e- Mg  Mg2+ +2e-

Put the
e- in.
Reduced – gain of e- O +2e-  O2-
 ELECTROCHEMICAL CELLS & ELECTRODE
POTENTIALS

 We can gain an understanding of these reactions

from a knowledge of electrochemical cells &
electrode potentials.

 we will discuss electrochemical cells, standard

electrode potentials, the Nernst equation (which
describes electrode potentials) etc.

10
Oxidation-Reduction reactions

 In many important chemical reactions, electrons are

transferred from atom to atom.

 They are easiest to deal with if we divide the overall

reaction into two half - reactions.

11
Oxidation-Reduction reactions

 In one half-reaction, electrons are LOST; this is called the

OXIDATION half – reaction. eg
a) NaNa++ e—
b) Fe2+Fe3++ e—
 In each case, the reactant is losing electrons.

 In the other half-reaction, electrons are GAINED; this is

called the REDUCTION half -reaction.
Eg Cu2++ 2e— Cu

12
Oxidation-Reduction reactions

 So what is involved in redox rxn?

 In a redox reaction, one reactant is a reducing agent (ends
up being oxidized) the other is an oxidizing agent (ends
up being reduced).
Fe2++ Cl2 Fe3++ 2Cl-
 Fe2+, the reducing agent, is reducing Cl2; the Fe2+ is
oxidized.
 Cl2, the oxidizing agent, is oxidizing Fe2+; the Cl2 is
reduced

13
Oxidation-Reduction reactions

 Reduction & oxidation always go together; one cannot

occur without the other.

 Notice that there are no electrons in the “overall”

equation......
 In any REDOX reaction, the electrons lost in the oxidation
half -reaction must exactly equal those gained in the
reduction half -reaction.

14
 GCSE
Oxidation: Reduction:
•Gain of oxygen •Loss of oxygen
•Loss of electrons •Gain of electrons

Increase in Decrease in
oxidation oxidation
number number
Oxidation-Reduction reactions

 OXIDATION NUMBERS
 Oxidation number (O.N.) is also known as oxidation state.

 the total number of electrons that an atom

either gains or loses in order to form
a chemical bond with another atom.

 You should be able to assign ON to elements!

16
Oxidation-Reduction reactions

 RULES FOR ASSIGNING OXIDATION NUMBERS

 O.N is always zero in the pure element or diatomic
molecule: (H2 (g), Cl2 (g) , Na (s) etc)

 In monatomic ions, the ON is equal to the charge on the

ion.

 In a neutral molecule, the total charge on the molecule

must be equal to 0.
H - Br: (+1) + (-1) = 0
PBr5 : (+5) + 5(-1) = 0

17
Oxidation-Reduction reactions

 In a complex ion, the total charge must be equal to the

charge on the ion.
NH4+: (-3) + 4(+1) = +1
ClO4—: (+7) + 4(-2) = +1

18
Oxidation-Reduction reactions

 Priority Rules (Memorize these!!!)

These rules, based on the electronegativity scale are
useful in assigning Oxidation Numbers in a
compound:
 Fluorine is always -1 in all compounds.
 Group I metals (Na, K, etc.) always +1
 Group II metals (Ca, Mg, etc.) always +2
 Group III metals its +3.

19
 Oxidation-Reduction reactions

 H is always +1 except when combined with a metal

to form a hydride
LiH is [Li+] [H-]; therefore H is -1
 Oxygen is always -2 except:
When combined with fluorine OF2: O is +2 (because F
is -1)
In Peroxides which contain the O-O bond
Eg such as H - O - O – H (Hydrogen Peroxide), where
O is -1
Na2O2 : is 2Na+ [O -O]2-, therefore O is -1
20
 Oxidation-Reduction reactions

 Other Halogens (Group VII) are always -1, except

when combined with fluorine or oxygen.....
BrF5: Br is +5 Cl2O: Cl is + 1
Examples
Assign oxidation states,CaCO3
C = 0-(+2)-3(-2) = +4
NaHSO4, S = 0-(+1)-(+1)-4(-2) = +6

21
BALANCING REDOX EQUATIONS

 When balancing Redox reactions, make sure that

the number of electrons lost by the reducing agent
equals the number of electrons gained by the
oxidizing agent
 Two methods can be used:
 Half-reaction method (Ion-electron method)
 Oxidation number method

22
Points to remember:

1) Electrons NEVER appear in a correct, final

answer.
 In order to get the electrons in each half-
reaction equal, one or both of the balanced half-
reactions will be multiplied by a factor.
2) Duplicate items are always removed. These items
are usually the electrons, water and hydroxide
ion.

23
BALANCING REDOX EQUATIONS

 Method 1: Half-reaction method

 RedOx reaction can occur either in ACIDIC solution
or BASIC solution.
 Example
 Permanganate ion oxidizes oxalate ions in ACIDIC
solution:
 MnO4— + C2O42— Mn2++ CO2

24
I. Balancing Redox Reactions

STEP 1. Split Reaction into 2 Half-Reactions

STEP 2. Balance Elements Other than H & O

STEP 3. Balance O by Inserting H2O into eqns. as

necessary

STEP 4. Balance H with H+ or H2O

 I. Balancing Redox Reactions

STEP 5. Balance Charge by Inserting Electrons as

needed

STEP 6. Multiply Each 1/2 Reaction by Factor

needed to make no. of Electrons in each 1/2
Reaction Equal

STEP 7. Add Eqns. & Cancel Out Duplicate terms,

where possible
 BALANCING REDOX EQUATIONS

Overall Reaction:
MnO4— + C2O42— Mn2++ CO2
 
Separate the reaction into two half-reactions:
MnO4— Mn2+
C2O42— CO2
Now, deal with each half reaction individually:

27
 BALANCING REDOX EQUATIONS

1) Balance non-O and non-H atoms as usual

MnO4— Mn2+ ,its fine, Mn balanced
C2O42— CO2
C2O42— 2CO2
2) Add H2O to balance oxygen
MnO4— Mn2+ + 4H2O
C2O42— 2CO2
3) Add H+ to balance H atoms (regardless of acidic or
basic)
MnO4— + 8H+Mn2++ 4H2O
CO 2—
2CO 28
 BALANCING REDOX EQUATIONS

4) Add electrons to balance the charge..electrons

added to the more positive side.
MnO4— + 8H+Mn2++ 4H2O
MnO4— + 8H+ + 5eMn2++ 4H2O
 Since e—appear on the left, this is REDUCTION
(gain of electrons).
 Mn goes from Oxidation Number +7 to Oxidation
Number +2 ; "it has gained 5 e

29
BALANCING REDOX EQUATIONS

C2O42— 2e + 2CO2

Since e—appear on the right, this is OXIDATION loss
of electrons).
C O.S changes positively!!

5) Multiply Each 1/2 Reaction by Factor needed to

make no. of Electrons in each 1/2 Reaction Equal
x 2 |MnO4— + 8H+ + 5eMn2++ 4H2O
x 5| C2O42— 2e + 2CO2

30
BALANCING REDOX EQUATIONS

2MnO4— + 16H+ + 10e2Mn2++ 8H2O

5C2O42— 10e + 10CO2

2MnO4— + 16H+ + 5C2O42— 2Mn2++ 8H2O + 10CO2

31
 I. Balancing Redox Reactions
(continued)
Example
Complete and Balance Following Reaction:
CuS (s) + NO3 - (aq) Cu2+(aq) + SO42- (aq)
+ NO (g)
STEP1. Split into 2 Half-Reactions

a.1 CuS Cu2+ + SO42-

b.1 NO3 - NO
 I. Balancing Redox Reactions
(continued)
STEP 2. Balance Elements Other than H & O
Already O.K. !
 I. Balancing Redox Reactions
(continued)
STEP 3. Balance O by inserting H2O into
equations as necessary

a.3 CuS + 4H2O Cu2+ + SO42-

b.3 NO3- NO + 2H2O

 I. Balancing Redox Reactions
(continued)
STEP 4. ACIDIC, so Balance H by inserting
H+ as needed

a4. CuS + 4H2O Cu2+ + SO42- + 8H+

b4. NO3- + 4H+ NO + 2H2O

 I. Balancing Redox Reactions
(continued)
STEP 5. Balance Charge by inserting
Electrons, where necessary

a5. CuS + 4H2O Cu2+ + SO42- + 8H+ + 8e-

b5. NO3- + 4H+ + 3e- NO + 2H2O

 I. Balancing Redox Reactions
(continued)
STEP 6. Multiply each Eqn. by factor to make
No. of Electrons in Each 1/2 Reaction the
Same
a6. Multiply by 3x
3CuS + 12H2O 3Cu2+ + 3SO42- + 24H+
+ 24e-
b6.Multiply by 8x
8NO3- + 32H+ + 24e- 8NO + 16H+
+ 24e-
 I. Balancing Redox Reactions
(continued)
STEP 7. Add Eqns. and Cancel Out
Duplicated Terms

(a7 + b7)
8H+
3CuS + 12H2O + 8NO3- + 32H+ + 24 e-
3Cu2+ + 3SO42- + 24H+ + 8NO +16 H2O
+24e- 4H2O
I. Balancing Redox Reactions
(continued)

So, the final, balanced reaction is:

3CuS(s) + 8 NO3-(aq) + 8H+ (aq)
3Cu2+(aq) + 3 SO42-(aq) + 8NO(g) +
+ 4H2 O(l)
 Checking mass balance and
charge balance in Equation
L.H.S R.H.S.
3 x Cu 3 x Cu
3 x S 3 x S
8 x N 8 x N
24 x O 24 x O
8 x H 8 x H

(8 x 1-) + (8 x H+) = 0 (3 x 2+ )+(3 x 2- ) = 0

Balancing redox reactions in basic solution

 In basic solutions, there is an excess of OH- ions.

The balanced reaction needs to be modified to
remove the H+ ions & include OH- ions.

41
Balancing redox reactions in basic solution

 Balance the following redox reaction in basic

conditions.
Ag(s)+Zn2+(aq)→Ag2O(aq)+ Zn(s)
Solution
 Go through all the same steps as if it was in acidic
conditions.

42
Balancing redox reactions in basic solution

 Step 1: Separate the half-reactions. 

Ag(s)→Ag2O
Zn2+(aq)→Zn(s)

Step 2: Balance elements other than O and H.

2Ag(s)→Ag2O(aq)
Zn2+(aq)→Zn(s)

43
Balancing redox reactions in basic solution

44
Balancing redox reactions in basic solution

45
Balancing redox reactions in basic solution

 Examples
Br¯ + MnO4¯ ---> MnO2 + BrO3¯
AlH4¯ + H2CO ---> Al3+ + CH3OH

46