The remaining notes on Redox Reaction

Balancing of Redox reactions

There are two ways of balancing Redox reactions:

 Oxidation number method

 Half equation method

Oxidation method: The steps to be followed-

1. Write the skeletal equation of reactants and products.

2. Indicate the oxidation number of all the elements involved in the reaction.
3. Calculate the increase or decrease in oxidation number per atom. Also, identify
the oxidizing and reducing agents.
4. Multiply the formula of oxidizing agent and reducing agent by suitable integers,
so as to equalize the total increase or decrease in oxidation number as
calculated in step c.
5. Balance all atoms other than H and O.
6. Finally balance H and O atoms by adding water molecules using hit and trial
method.
7. In case of Ionic reactions:

 For acidic medium

 First balance O atoms by adding water molecules to the deficient side.
 Balance H+ ions to the side deficient in H atoms.
 For Basic medium
 First balance oxygen atom by adding water molecules to the deficient side.
 Then to balance hydrogen, add water molecules equal to the number of
deficiency of H atoms.
 Also add equal number of OH- ions to opposite side of the equation.

Example: Permagnate ion reacts with bromide ion in basic medium to give manganese
dioxide and Bromate ion .

Step1: the skeletal ionic equation is :

MnO4- (aq) +Br- (aq) ---> MnO2 +BrO3-

Step 2: assign oxidation numbers for Mn and Br

Step3: calculate the increase and decrease in oxidation number and make the change
equal :
Step: 4 as the reaction occurs in basic medium, and the ionic charges are not equal on
both sides, add 2OH- ions on the right to make it equal.

Step5: finally count the hydrogen atoms and add appropriate number of water
molecules on the left side to achieve balanced Redox reaction.

Half reaction method or Ion electron method

1. Write the skeletal equation and indicate the oxidation number of all the elements
which occur in skeletal equation
2. Find out the species that are oxidized and reduced.
3. Split the skeletal equation into two half reactions: oxidation half reaction and
reduction half reaction
4. Balance the two-half equation separately by rules described below:

 In each half reaction first balance the atoms of element that has undergone a
change in oxidation number.
 Add electrons to whatever side is necessary to make up the difference in
oxidation number in each half reaction.
 Balance the charge by adding H+ ions, if the reaction occurs in acidic
medium .For basic medium, add OH- ions if the reaction occurs in basic medium.
 Balance oxygen atoms by adding required number of water molecules to the side
deficient in oxygen atoms
 In the acidic medium, H atoms are balanced by adding H + ions to the side
deficient in H atoms.
 However, in the basic medium H atoms are balanced by adding water molecules
equal to number to H atoms deficient.
 Add equal number of OH- ions to opposite side of equation.
 The two half reactions are then multiplied by suitable integers .so that the total
number of electrons gained in half reaction becomes equal to total number of
electrons lost in another half reaction.
 Then the two half reactions are added up.
 To verify the balancing, check whether the total charge on either is equal or not.

Example: Let us consider the skeletal equation:

Fe2+ + Cr2O72- --> Fe3+ +Cr3+

Step 1: Separate the equation in to two halves:

Oxidation half reaction: Fe2 --> Fe3+

Reduction half reaction: Cr2O72- --> Cr3+

Step 2: Balance the atoms other than hydrogen and oxygen in each half reaction
individually. Here the oxidation half reaction is already balanced with respect to Fe
atoms .For the reduction half reaction, we multiply the Cr3+ by 2 to balance Cr atoms.

Step 3: For reactions occurring in acidic medium, add water molecules to balance
oxygen atoms and hydrogen ions are balanced by adding H atoms. Thus, we get:

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

Step 4: Add electrons to one side of the half reaction to balance the charges .if needed
make the number of electrons equal in two half reactions by multiplying one or both half
reaction by suitable coefficient.

The oxidation half reaction is thus written again to balance the charge .Now in the
reduction half reaction there are 12 positive charges on the left hand side and only 6
positive charge on right hand side .Therefore, we add six electrons to left hand side .

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

To equalize the number of electrons in both reactions, we multiply oxidation half

reaction by 6 and write as:

6Fe2+ --> 6Fe3+ +6e-

Step 5: We add the two half reactions to achieve the overall reaction and cancel the
electrons on each side .This give us net ionic equation:

6Fe2+ + Cr2O72- + 14 H -->

+ 2Cr3++6Fe3+ +7H2O

Step6: Verify that the equation contains the same type and number of atoms and the
same charges on both sides of the equation. This last check reveals that the equation is
fully balanced with respect to number atoms and the charges.

Types of Redox reactions

1. Combination reaction: When two or more reactants react to form single

product.

i.e a + b --> ab (in this single product is formed).

For the reaction to be Redox, both the elements should be in elemental form.

For example: All combustion reactions are Redox reactions.

C0 + O2 --> CO2

Carbon Oxygen Carbondioxide

 2. Decomposition reaction: It is the type of reaction, in which a reactant breaks up
into its constituents either by heating, passing current or in presence of light.

2. Displacement reaction: It is the reaction between element and a compound. In

This more reactive element displaces less reactive from its compound.

CuSO4 + Zn --> ZnSO4 + Cu

Copper Sulphate Zinc Zinc Sulphate Copper

Displacement reactions fit into two categories: metal displacement and non metal
displacement.

Metal displacement: a metal in a compound can be displaced by another metal in the

uncombined state .Metal displacement reactions find many applications in metallurgy.
Few examples are:

Non-metal displacement: The non metal displacement involves mainly displacement of

hydrogen and a rarely occurring reaction involving oxygen displacement .For example:

Non metal non-metal displacement: in this non metal gets displaced by non metal
according to reactivities .For example if we consider fluorine and chlorine so, it is but
obvious that fluorine can replace chlorine as it is more reactive.

4. Disproportionate reaction: A reaction in which the same species is

simultaneously reduced and oxidized .One of the reacting species in this reaction
is always an element, that can exist in at least three oxidation states .The
element in the form of reacting species is in the intermediate oxidation state .In
this higher and lower both oxidation states of the element are formed.
5. For Example:-

H2O2 --> H2O + H2

Hydrogen Peroxide Water Oxygen Gas

In above example, the oxidation number of Oxygen which is -1 in peroxide increases to

zero in O2 and decreases to -2 in water.

There are two types of Redox reactions

 Direct Redox reaction

 Indirect Redox reaction

Direct Redox reaction: In which oxidation and reduction both occur in same beaker. In
this electron so produced does not travel to large distance.

For example: A beaker containing Zinc rod dipped in Copper sulphate solution in this
the following reaction occur:

Zn + CuSO4 --> ZnSO4 + Cu

Zinc CopperSulphate Zinc Sulphate Copper

In this zinc being more reactive displaces copper from copper sulphate and forms zinc
sulphate and copper.

Indirect Redox reactions: In it oxidation and reduction occur in different beakers. The
electron so produced has to travel a certain distance that leads to generation of current.

Example: Daniel cell: A cell containing Zn-Cu couple that we are going to study in detail
now as given below but before that let us make you familiar with the general term used
in redox reaction that is Redox couple

Redox couple

It is defined as having together the oxidized and reduced forms of a substance taking
part in oxidation or reduction half reactions .they are actually conjugate acid base
pairs .we can also define it as : an oxidizing and reducing agent which appear on
opposite sides of a half equation constitute the redox couple .Like, given below is the
cell in which we consider Zn/Cu redox couple .

Electrochemical cell

 Electrochemical cell is the cell in which chemical energy gets converted to

electric energy.
 In it indirect redox reactions takes place.
 These reactions are spontaneous that is free energy change for this reaction is
negative.
 This cell consists of two half cells.
 In one half cell , there is a aqueous 1molar Zinc sulphate solution with Zinc rod
dipped in it.
 In other half cell, there is a 1 molar aqueous solution of Copper sulphate solution
with Copper rod dipped in it.
  These electrodes by means of wire are attached to galvanometer.
 A U-shaped tube is taken, which is sealed from both the ends with cotton plug.
 In this, the electrolyte that is inert electrolyte is taken like Potassium nitrate,
Ammonium nitrate etc. The electrolyte present is in semi-liquid state.

Observations

 With time we see that Zinc rod loses weight, as it has more tendency to loose
electrons that is:

Zn -2 electrons --> Zn2+ (Oxidation)

Zinc Zinc Ion

 These electrons released by zinc, travel to another beaker by means of wire. In

doing so, they cause deflection in galvanometer and produce current. This
current travel in the direction opposite to the flow of electrons.
 These electrons move to another half cell, where copper ions gain these
electrons that is reduction occur. As a result, copper metal start depositing on
electrode. The reaction that occurs is shown below:

Cu2+ + 2electrons --> Cu(reduction)

Copper ions Copper Metal

Functions of salt bridge

 It connects the circuit internally by connecting the solutions.

 It helps in maintain neutrality.

With passage of time, the left container will have excess positive charge around
electrode. Due to which further oxidation stops .Whereas in other beaker negative
charge will exceeds, which will start repelling electrons. Therefore, at that time salt
bridge comes into action. The oppositely charged electrolyte ions start diffusing into half
cells in order to neutralize the excess charge. Hence, the cell keeps on working.
The electrolyte that is selected must fulfill two conditions:

 Size of its cation and anion should be equal.

 Electrolyte in salt bridge should not interact with the main electrolyte of half cells.

The overall reaction that takes place is:

Zn + Cu2+ --> Zn2+ + Cu

Zinc Copper Zinc Ion Copper Metal

Representation of the cell

Formula to calculate standard electrode potential of cell (when concentration of

electrolyte is 1 molar)

E=Ec-Ea (where ‘c’ is cathode and ‘a’ is anode).

Electrode potential

Electrode potential is defined as “potential difference set up between electrode and

electrolyte of same beaker”.

It is of two types:

 Reduction potential: Tendency of solution to get reduced.

 Oxidation potential: Tendency of electrode to get oxidized.

Factors on which electrode potential depends:


 Concentration of ions in solution.
 Nature of metal and its ions.

Electromotive force

It is the potential difference between two electrodes when no current flows through the
circuit.