Unit 7 Electrochemistry

Unit 7

INTRODUCTION

Oxidation-reduction reactions (redox) are fundamental chemical processes that play a crucial role in a variety of
natural phenomena and industrial applications.

This chapter examines Cine commonalities between different redox reactions, such as the frusting of iron
objects, the burning of fuel in car engines) forest fires, and (the metabolism of food in human and animal bodies
in addition, the importance of redox reactions in the production of electricity in batteries, in the decolorization
of substances with household bleaches, and in the industrial production of important metals and chemicals is
discussed.

One of the most important application of electrochemistry is batteries and fuels cells, which use chemical energy
to generate electrical energy.

OXIDATION AND REDUCTION

We can define redox reactions in terms of transfer of oxygen, hydrogen, and electrons. In redox reactions
oxidation and reduction occur simultaneously.

Oxidation-Reduction in Terms of Loss or Gain of Oxygen, Hydrogen or Electrons

Oxidation is gain of oxygen and reduction is loss of oxygen

In steel mills iron ores, usually oxides of iron are converted to the pure metal commercially by the reaction with
coke (carbon) in the blast furnace. The carbon first reacts with air to form carbon monoxide, which in turn reacts
with iron oxide as follows.

Fe₂O₃ +3CO→ 2Fe + 3CO₂

Which substance... this reaction is losing oxygen? Which substance is gaining oxygen?

CO is gaining oxygen, so undergoing oxidation. Fe₂O, is losing oxygen, so undergoing reduction.

Oxidation-reduction in terms of transfer of hydrogen

Oxidation is loss of hydrogen and reduction is gain of hydrogen

Acetylene (C₂H₂) is commercially used for cutting and welding metals. When acetylene burns, it produces a very
hot flame known as oxy-acetylene flame. Following reaction takes place when it burns.
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2C₂H₂ +502 4CO₂ +

Ovidiation Reduction 2H2O→ Grin of Gain af

Which substance is losing hydrogen? Which substance is gaining hydrogen?

C,H, is losing hydrogen, so unregoing oxidation. O, is gaining hydrogen, so undergoing reduction.

Loss the foes

Oxidation and Reduction in Terms of Transfer of Electrons

Oxidation is loss of electrons and reduction is gain of electrons. For example, consider the following reaction.

CuO + Zn Cu + ZnO

Copper (II) oxide and zinc (II) oxides are both ionic compounds. Rewrite this equation as forc equation.

CuO+Zn

With Zn² + O2

Oxide ions are spectator ions, so net equation is;

With

+ Zn

Cu + Zn²

Cu ions are gaining 2 electrons to form Cu. Its oxidation state changes from +2 to zero. So C are undergoing
reduction. The oxidation number of Zn is increasing from zero to +2, so Zn is losing
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2 electrons and undergoing oxidation.

Oxidation is defined as the loss of hydrogen, gain of oxygen or loss of electrons.

Reduction is defined as the gain of hydrogen, loss of oxygen or gain of electrons.

Example 7.1: Identifying the element undergoing oxidation in terms of transfer of oxygen or hydrogen

Following reaction occurs when you burn Sui gas.

CH₄ +20₂→ CO2 + 2H2O + heat

Identify the element undergoing oxidation.

Problem solving strategy:

Identify the substance that gains O-atoms or loses H-atoms.

Solution:

Since C in CH, loses H-atoms and combines with oxygen atoms, thus C atoms undergo oxidation. At the same
time O-atoms combine with H-atoms to form H₂O, thus O-atoms undergo reduction

Redox in photography

A photographic film is basically an emulsion of silver bromide, (AgBr) in gelatin. When

the film is exposed to light. Silver bromide granules become activated. This activation
depends on the intensity of the light falling upon them. When exposed film is placed in the
developer solution that is actually a reducing agent. Hydroquinone which is a mild
reducing agent is used as developer. In hydroquinone the activated granules of silver
bromide are reduced to black metallic silver. Reduced silver atoms form image.

Ag+1e Agm

Inactivated silver bromide is removed from the film by using a solvent called a fixer.
Sodium thiosulphate is used for purpose. The areas of the film exposed Ito the light
appear darkest because they have the highest of metallic silver. Thus photography
involves oxidation-reduction reaction. concentration
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CONCEPT ASSESSMENT EXERCISE 7.1

Identify elements undergoing oxidation and reduction in the following reactions:

1. N₂+3H2NH,

2. 2H₂+0₂→ 2H₂O

3. Fe₂O₃+3CO→ 2Fe+ 3CO₂

4. 4Al +3022Al2O3

Example 7.2: Identifying the element oxidized or reduced in terms of transfer of electrons

In the following reaction identify which element is oxidized and which element is reduced 2Ca + O2 2CaO

Problem solving strategy:

Ca being metal forms cation by losing electrons (oxidation) and oxygen being non-metal gains electrons
(reduction) to form anion.

Solution:

Remember that Group IIA metals form M² cations, and that Group VIA non-metals form X² anions. This means in
this reaction each Ca atom loses two electrons to form Ca²", so it is oxidized. Each oxygen atom gains two
electrons to form O², so it is reduced. 2Ca2Ca2+ + 2e (oxidation) O2+4e202 (reduction)

CONCEPT ASSESSMENT EXERCISE 7.2

In the following reactions, identify which element is oxidized and which element is reduced in terms of electron
transfer.

010 4Na+O2→ 2Na₂O 2Al + 3Cl2→2AlCl3 Mg+Cl₂→ MgCl₂

OXIDATION STATES AND RULES FOR ASSIGNING OXIDATION STATES

Oxidation States

Oxidation state or oxidation number is defined as the number of charges an atom will have in a molecule or a
compound
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The elements that show an increase in oxidation number are oxidized.

The elements that show a decrease in oxidation number are reduced.

Do you think H in HCl is oxidized and Cl is reduced?

Comparison of oxidation and reduction processes

Oxidation Reduction

Gain of oxygen Loss of oxygen

Loss of hydrogen Gain of hydrogen

Loss of electrons Gain of electrons

Increase in oxidation number Decrease in oxidation number

7.2.2 Rules for Assigning Oxidation States or Numbers

The oxidation state of any uncombined or free elements is always zero e.g., oxidation state of Zn, Na, H in H,, S
in S, etc is zero.

In simple ions, oxidation state is same as their charge e.g., oxidation state of Na in Na"and

Ca in Ca" is +1 and +2 respectively.

2. 3.4 In a complex ion the sum of oxidation states of atoms is equal to the charge on their ion. e.g., in CO,', the
sum of oxidation states of C and 30 atoms is -2. Similarly, in NH", the sum of oxidation states of N and 4H atoms
is +1.

The oxidation number of each of the atoms in a molecule or compound is counted separately and their algebraic
sum is zero e.g., In HCl, the sum of oxidation states of Hand Cl atoms is zero. Similarly in CO₂, the sum of
oxidation states of one C and 2 oxygen atoms 2 is zero./

Table 7.2 shows the oxidation states of some of the elements in binary compounds which rarely change.

Table 7.2: Oxidation states of some elements in binary compounds that rarely change

Elements

Oxidation State

Group-IA
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+1

+2

Group-IIA

Group-IIIA

+3

H+1

(except in metal hydrides where it is -1)

Group-VIIA

-1

GV1-2 (except peroxides and in OF₂)

Monoatomic ions and their oxidation numders

The oxidation number of a monatomic ion is equal to its charge.

For example, Na' is formed after a Na atom has lost one electron to gain a +1 charge. So its oxidation number is
+1. Similarly number is -1. The oxidation number of an atom is the number of electrons the atom has lost or
gained. Because a monatomic ion is formed by the gain or loss of electrons from a single atom, charge is equal
to its oxidation number..
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Polyatomic ions and their oxidation numders

In a polyatomic ion, the sum of the oxidation numbers of all the atoms is equal to the charge on the lon. For
example, in CO, lon the oxidation numbers of carbon and oxygen are +4 and -2 respectively. So, the sum of the
oxidation number of one carbon atom and three oxygen atoms would be 1(+4)+3(-2)=-2 which is the charge on
the ion.

7.2.3 Determining the Oxidation Number of an Atom in a Compound

Let's see how to use rules discussed in section 7.2.2 to determine the oxidation number of an atom of an
element in a compound.

Example 7.3: Determining oxidation number

A device called Breathalyzer is used by police to test a person's breath for alcohol. It contains an acidic solution
of potassium dichromate K₂Cr₂O,. It is a strong oxidizing agent. Determine oxidation state of Cr in it.

Problem Solving Strategy:

Use rules 1 to 4 and table 7.1 to get as many oxidation numbers as you can. Use rule 4 to get oxidation number
that has not b

Solution:

1. The oxidation number of K is +1, since it belongs to Group-1A. There are 2 K atoms therefore, overall
oxidation number for K is 2(+1) =+2

2. There are 7 oxygen atoms, therefore overall oxidation state for O is 7(-2) = -14

3. Suppose oxidation for Cr is x, since there are two Cr atoms, therefore, overall oxidation sate for Cr is 2x.

4. The sum of oxidation numbers must be zero. +2+2x+(-14) = 0 2x-12 = 0 2x = 12 x = +6 Thus oxidation state for
Cr in K₂Cr₂O, is +6

Example 7.4: Determining oxidation state

Boric acid H,BO, is used in eye wash. What is the oxidation state of B in this acid?

Problem solving strategy:

✓ Use rules and table 7.2 to get the oxidation state of H and O- atoms. Use rule 4 to Bet the oxidation state of B.

Solution:

1. There are 3 H-atoms, therefore, overall oxidation state for H is 3(+1) = +3

2. There are 30-atoms, therefore, overall oxidation state for O is

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3-2)6

Suppose the oxidation state for B is x.

4. The total oxidation states for all the atoms must be zero. +3+x+(-6)-0 +3+x-6-0 x-3-0

x-3

Thus the oxidation state for B in H,BO, is 3.

and Q8.

CONCEPT ASSESSMENT EXERCISE 3.1

One major problem of air pollution is the formation of acid rain. Air pollutants such as 50, NO, combine with
oxygen and water vapours in the air to form H,SO, and HNO, These acids fal the ground with the rain, making
the rain acidic. Clouds can also absorb the acids and carry the hundreds of kilometers away from where the
pollutants are released. Determine the oxidate number of N in NO, and HNO,, S in SO, and H,SO,

Example 7.5: Determining the oxidation number of an element in an ion.

What is the oxidation number of C in carbonate ion, Co,

Problem Solving Strategy:

(a) Use rule that oxidation number of O is -2

(b) Use rule 3 to find oxidation state of C

Solution:

Oxidation State of one C-atom Oxidation state of 3-0 atoms = -2

Oxidation state of C-atom 3(-2)-2

Oxidation state of C-atom-6-2

Oxidation state of C-atom--2-6

Oxidation state of C-atom +4

Thus the oxidation of C in carbonate ion is +4

CONCEPT ASSESSMENT EXERCISE 7.4

Determine the oxidation state of

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S in sulphate lon, 50,

2 P in phosphate lon, PO,

1. N in ammonium Ion, NH,"

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7.3 FORMULA OF AN IONIC COMPOUND

To determine the formula of an ionic compound from the ionic charges and oxidation numbers of the
constituent lons, you must determine the simplest whole-number ratio of cations (positively Charged ions) to
anions (negatively charged ions) that results in a neutral compound. Ionic compounds are electrically neutral,
meaning that the total positive charge of the cations is equal to the total negative charge of the anions. Let's go
through step by step to derive the formula:

Example: Calcium chloride

Step 1: Identify the lons in the compound and their charges. Consider, for example, the combination of calcium
ions (Ca") and chloride ions (CI).

Step 2: Determine the ratio of charges needed to balance each other. In this case, calcium has a charge of +2 and
chloride has a charge of -1. You need two chloride ions for every calcium ion to balance the charges.

Step 3: Write a formula with assignments that represents the relationship defined in Step 2. The formula for
calcium chloride is CaCl₂.

Example: Magnesium oxide

Step 1: Identify the ions and their charges - magnesium ions (Mg") and oxide ions (0)

Step 2: Determine the charge - the magnesium has a charge of 2 and the oxide has a charge of -2. Thus, one
magnesium ion is required for each oxide ion.

Step 3: Write the formula - MgO.

Example: Aluminum sulphate

Step 1: Identify the ions and their charges-aluminum ions (Al") and sulphate ions (SO,¹)

Step 2: Determine the charge - aluminum has a charge of +3 and sulphate has a charge of -2. You need two
aluminum ions for every three sulphate ions to balance the charges.

Step 3: Write the formula - Al2(SO4)3.

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It is important to remember that when writing a formula, parentheses must be used to add polyatomic ions
when more than one is needed to balance the charges. By following these steps and understanding the charges
on the ions, you can derive the formulas of various ionic compounds.

7.3.1 Use of Roman numerals as oxidation number

Roman numerals are used to indicate the oxidation states of elements in compounds, when a metal exhibits
variable oxidations in compounds. For examples in transition metal compounds. Cu50, is written as copper (II)
sulphate.

FeCl, is written as iron (II) chloride.

FeCl, is written as iron

(III) chloride

7.4 OXIDIZING AND REDUCING AGENTS

An oxidizing agent is a substance that causes another substance to oxidize by taking electrons from iting agent is
a substance that cacceptor because it accepts electrons during a reaction.

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Oxidizing agents themselves are reduced in the process (they gain electrons). Examples of common oxidizing
agents are oxygen (O,), hydrogen peroxide (H,O,), chlorine (Cl,) and potassium maxidizing agents reducing agent
is a substance that causes another substance to be Peugeot it. It is often called an electron donor the cause it
love, electrons during the reaction. The reducing agents themselves are oxidized in the process (the) lose
electrons). Examples of common reducing agents include hydrogen gas (H₂), metal hydrides (such as NaBH,),
carbon monoxide (CO), and metals such as zinc (Zn) and aluminum (Al). it.

For example, in the reaction between sodium and chlorine to form sodium chloride. 2Na + Cl2 → 2NaCl Na is
reducing agent as it is oxidize whereas Cl, is oxidizing agent as it is reduced.

Activity 7.1

Prepare solutions of ferrous sluphate(FeSO,) and potassium permanganate (KMnO,) in separate beakers.
Transfer about 10cm³ of ferrous sulphate solution in a test tube. Add about 10cm² of dill. H,SO, in it. Now add
few drops of KMnO solution in the test tube. What happens?

FeSO reduces KMnO,, so its purple colour is discharged. KMnO, oxidizes FeSO, in this reaction.

FeSO, is reducing agent whereas KMnO is oxidizing agent

A color change during a chemical reaction may indicate a redox reaction.

Unit 7 Electrochemistry

Potassium permanganate (VII) is an oxidizing agent.

Often used to test for the presence of reducing agents.

When acidified KMnO, is added to the reducing agent, it changes from purple to colorless.

The above reaction discharges the purple colour of KMnO

Therefore, the solution must contain a reducing agent that reduces MnO2 ions (purple) to Mn ions (colourless).

During this reaction, the oxidation number of Mn changes from +7 to +2.

Activity 7.2

Prepare an aqueous solution of potassium iodide and transfer it to a 10 cm³ test tube.
Add abou 5 cm³ of hydrogen peroxide to it. what's going on, the solution turns reddish-
brown, indicatin the formation of iodine.

Potassium iodide is a reducing agent. Often used to test for the presence of oxidizing
agents solution potassium iodide solution is added to an acidified the presence of
oxidizing on solution turns reddish-brown. The appearance of this color is due to the
formation of iodinel

KI is oxidized and H₂O, is reduced. This redox reaction can be confirmed by a color change from colorless to
reddish-brown. H₂O)+2KI+2H, 2K(aq) + 2(aq) + 2H₂O

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Unit 7: Electrochemistry

7.4.2 How can you identify oxidizing and reducing agents in a chemical reaction?

Consider the following reaction that takes place in the manufacture of steel.
Unit 7 Electrochemistry

Fe₂O₃ + 3CO2Fe +3CO,

To identify the oxidizing and reducing agents, work out the oxidation states of all the elements involved in the
reaction.

2(+3)

(-2)3

+2-2

+4(-2)2

0 Fe₂O₃ + 3CO→2Fe + 3CO₂

Carbon is being oxidized because there is an increase in its oxidation state.

(i)

(ii) Fe is being reduced because there is a decrease in its oxidation state.

(iii) The reactant CO contains the C that is being oxidized, so CO is reducing agent.

(iv) The reactant Fe₂O, contains the Fe that is being reduced. So Fe₂O, is oxidizing

agent.
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Oxidizing or reducing agent is the whole molecule or formula unit and not the atom that has undergone change
in oxidation number.

Example 7.6: Identifying the oxidizing and reducing agents

Tungsten is used to make filaments for electric bulbs because it has the highest melting point and high electrical
resistance. This metal is obtained from tungsten (VI) oxide, WO3 by reducing it with hydrogen gas.

WO3 + 3H2

→W+3H₂O

Identify the oxidizing and reducing agents in this reaction.

Problem solving strategy:

Step 1: Workout the oxidation states of all the elements involved in the reaction.

Step 2: Note the element that is undergoing an increases in its oxidation state. Since it is being oxidized. The
reactant that contains this element is reducing agent.

Step 3: Note the element that is undergoing a decrease in its oxidation state. Since it is being reduced. The
reactant that contains this element is oxidizing agent.

Solution:
Unit 7 Electrochemistry

First assign oxidation numbers to each atom.

+6 (-2)3

2(+1)-2

WO3+3H2W+3H2O

Because the oxidation number of W decreases, so WO, is an oxidizing agent. Similarly the oxidation number of H
increases, therefore H₂is reducing agent.

CONCEPT ASSESSMENT EXERCISE 7.5

1. Identify oxidizing and reducing agents in the following reactions:

a) 25+Cl, →S,Cl,

b) 2Na +Br2NaBr

Differentiate between oxidizing and reducing agents.

Society, Technology and Science

Unit 7 Electrochemistry

Redox in photography

Silver is very soft metal. Silver atoms have weak interactions and are loosely packed togethas eggs, the Silver is
very soft metal actech trace quantities of H,S or SO, in the atmosphere or food such as eggs, that are nich air
subenut compounds. Silver tarnish is silver sulphide that gives silver blackish appearance. Due to this reason
decorative and practical objects made of solid silver gradually turn black and lose shining appearance. Decoratie
and practical objects are plated with a thin layer of silver. Atoms in thin layers firmly adhere to the metal atoms
of the object and form a durable layer. An article thickly plated with silver contains many layers of silver atoms.
Such layers form soft covering. These layers gradually turn black.

7.5 CORROSION AND ITS PREVENTION

Corrosion is a natural electrochemical process that occurs when a metal reacts with its environment. In this
reaction a metal reacts with oxygen and moisture in the atmosphere.

Corrosion converts refined metals to the more stable metal oxides. It can cause significant damage to structures,
vehicles, and equipments by the slow and continuous eating away of metals. .

Most familiar example of corrosion is the formation of rust on iron. Oxygen and water are necessary for iron to
rust. Corrosion is an oxidation-reduction reaction. A region of metal surface that has relatively less moisture,
acts as anode.

Will Fe oxidize in this region? Yes.

Fe(s) → Fe+2 (aq) + 2e-

Another region on the surface of metal that has relatively more moisture acts as cathode. The electrons released
in the oxidation process reduce atmospheric oxygen to hydroxyl ions.

O2 + 2H2O + 4e - ------ > 4OH

The Fe lons formed at the anodic regions flow to the cathodic regions through the moisture of on the surface.
Here Fe+2 ions further react with oxygen to form rust, Fe2O3.xH2O

Prevention of Corrosion
Corrosion is a widespread issue that affects industries, infrastructures, and everyday objects. Therefore,
understanding corrosion and implementing preventive measures are crucial. Prevention of corrosion is an
important way of conserving our natural resources.

Following methods have been devised to protect metals from corrosion:

Coating with paint:

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Corrosion can be prevented by applying protective coating such as paint or epoxy creating

a barrier between metal surface and its environment. Paint is cheap and can be applied easily. Paint is used to
protect many everyday steel objects such as cars, trucks, trains,

bikes, bridges etc. Paint also provides visual appeal. Alloying: (mixing of two metals)

The tendency of iron to oxidize can be greatly reduced by alloying it with other metals. For example, adding
chromium to iron forms stainless steel, which is highly resistant to corrosion.

Coating with a thin layer of another metal:

Metals that readily corrode can be protected by coating with a thin layer of another metal that resists corrosion.
This can be done by:

(a) Tinning (Pb)

(b) Galvanizing (2hcl2)

(c) Electroplating

(a) Tinning: In the process of tin plating, clean iron sheet is dipped in a bath of molten tin. It is then passed
through hot pair of rollers. Tin protects iron effectively, since, it is very stable.

(b) Galvanizing (Coating with Zinc): The process of galvanizing consists of dipping a clean iron sheet in a hot zinc
chloride bath and heating. After this sheet is rolled into zinc bath and cooled.

(c) Electroplating: In electroplating an electrolytic process is used to deposit one metal on another metal.

Cathodic Protection:

Cathodic protection also called sacrificial protection is the process in which the metal to be protected from
corrosion is made cathode and connected to an active metal such as magnesium or aluminum. These metals are
more active than iron, they act as anode. The more active metal oxidizes itself and saves iron from corrosion.
Cathodic protection is employed to prevent iron and steel structures such as pipes, tanks, oil rigs etc in the moist
underground and marine environment. The large bars of magnesium are used to help protect the ship against
rusting.

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Unit 7 Electrochemistry

KEY POINTS

Oxidation is the gain of oxygen atom or loss of hydrogen atom or loss of electrons by substance.

•Reduction is the loss of oxygen atom or gain of hydrogen atom or gain of electrons by substance.

⚫Oxidation state or oxidation number is defined as the number of apparent charges that an atom will have in a
molecule.

•The sum of oxidation state of all the atoms in a molecule of compound is zero.

•An oxidizing agent is the reactant containing the element that is reduced in a reaction.

•Areducing agent is the reactant containing the element that is oxidized in a reaction.

•Corrosion is the process in which a metal reacts with oxygen and moisture in the atmosphere

•Electrolytic process used to deposit one metal on another metal is called electroplating.

•Cathodic protection is the process in which metal that is to be protected from corrosion made cathode and is
connected to metals such as magnesium or aluminum.