ENGINEERING CHEMISTRY (R25)

Complete Comprehensive Solutions for Important Questions Bank

UNIT-I: Water and Its Treatment

Q1. Define hardness of water. Explain the types of hardness with suitable examples.

Hardness of Water: Hardness is defined as the characteristic property of water that prevents the lathering of soap.
It is primarily caused by the presence of dissolved salts of multi-valent metallic cations, predominantly Calcium
(Ca2+) and Magnesium (Mg2+), along with anions like bicarbonates, chlorides, and sulfates.

When soap (sodium salts of long-chain fatty acids like sodium stearate) is added to hard water, it reacts with these
cations to form an insoluble, sticky white precipitate called "scum", before generating lather:

2C17H35COONa (Soap) + Ca2+ → (C17H35COO)2Ca ↓ (Scum) + 2Na+

Types of Hardness: Hardness is classified into two distinct categories:

1. Temporary Hardness (Carbonate Hardness):

This is caused by the presence of dissolved bicarbonates of calcium and magnesium [Ca(HCO3)2 and
Mg(HCO3)2]. It is called temporary because it can be easily removed by simple boiling, which converts the
soluble bicarbonates into insoluble carbonates or hydroxides:

Ca(HCO3)2 →Δ CaCO3 ↓ + H2O + CO2 ↑

2. Permanent Hardness (Non-carbonate Hardness):

This is caused by the presence of dissolved chlorides and sulfates of calcium and magnesium [CaCl2, MgCl2,
CaSO4, MgSO4]. It is called permanent because it cannot be removed by boiling and requires specialized
chemical treatment processes (such as ion exchange or lime-soda processes) for removal.

Q2. Describe the principle, procedure, and calculations involved in the determination of
hardness of water by the EDTA complexometric titration method.

Principle: Ethylene Diamine Tetra Acetic Acid (EDTA) forms stable, soluble chelate complexes with Ca2+ and
Mg2+ ions at a specific pH of 10. Eriochrome Black-T (EBT) is used as an indicator. When EBT is added to hard

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 1

water at pH 10 (maintained using an NH4OH - NH4Cl buffer solution), it binds weakly with the metal ions to
form an unstable, wine-red colored metal-indicator complex:

M2+ (Ca/Mg) + EBT → [M-EBT] (Unstable Wine-Red Complex)

During titration against EDTA, the EDTA molecules displace EBT because the metal-EDTA complex is
significantly more stable. At the end-point, when all metal ions are complexed by EDTA, the free EBT indicator is
liberated, turning the solution color from wine-red to distinct steel blue:

[M-EBT] (Wine-Red) + EDTA → [M-EDTA] (Stable Colorless Complex) + EBT (Steel Blue)

Procedure:

1. Preparation of Standard Hard Water: Dissolve 1g of pure CaCO3 in minimum HCl and dilute to 1000 mL
(1 mL = 1 mg of CaCO3 equivalent).

2. Standardization of EDTA: Titrate 50 mL of standard hard water against EDTA using 2-3 drops of EBT and 5
mL of ammonia buffer until the wine-red color turns steel blue. Let the volume consumed be V1 mL.

3. Determination of Total Hardness: Repeat the titration using 50 mL of the unknown sample water. Let the
volume consumed be V2 mL.

4. Determination of Permanent Hardness: Boil 250 mL of the sample water to precipitate temporary hardness,
filter, cool, and dilute the filtrate back to 250 mL. Titrate 50 mL of this boiled sample against EDTA. Let the
volume consumed be V3 mL.

Calculations:

• 1 mL of Standard Hard Water = 1 mg of CaCO3 equivalent.

• Molarity / Strength of EDTA: V1 mL of EDTA = 50 mL of Standard Hard Water = 50 mg of CaCO3.

Therefore, 1 mL of EDTA = 50 / V1 mg of CaCO3 eq.

• Total Hardness: 50 mL of sample water = V2 mL of EDTA = V2 × (50 / V1) mg of CaCO3 eq.

Total Hardness = (V2 / V1) × 1000 × mg/L (ppm)

• Permanent Hardness: Derived from the boiled water titration volume V3:

Permanent Hardness = (V3 / V1) × 1000 × mg/L (ppm)

• Temporary Hardness: Calculated by subtracting permanent hardness from total hardness:

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 2

 Temporary Hardness = Total Hardness - Permanent Hardness = [(V2 - V3) / V1] × 1000 × ppm

Q3. What is potable water? Explain the various steps involved in the treatment of water
for domestic purposes.

Potable Water: Potable water is water that is safe, clean, and fit for human consumption and domestic use.
According to WHO specifications, it must be colorless, odorless, pleasant to taste, free from turbidity, chemically
balanced (pH 6.5–8.5), and entirely free from pathogenic micro-organisms and toxic chemicals.

Steps involved in the treatment of domestic/municipal water:

1. Screening: Raw water is passed through large screens to remove floating debris like leaves, wood pieces, and
plastic matter.
2. Aeration: Water is exposed to air to absorb oxygen, which oxidizes dissolved gases (like H2S and CO2) and
volatile organic matter, eliminating foul odors and tastes.
3. Sedimentation: Water is allowed to stand undisturbed in large tanks. Suspended heavy particles settle down by
gravity at the bottom.
4. Coagulation (Sedimentation with Coagulation): For finely divided colloidal impurities that do not settle
easily, coagulants like Alum [Al2(SO4)3] are added. They form a gelatinous precipitate of Al(OH)3 that traps
and flocs fine particles together, facilitating quick settling.
5. Filtration: The water is passed through sand and gravel beds (such as slow sand or rapid sand filters) to
remove remaining fine particles, suspended matter, floccules, and a significant portion of bacteria.
6. Disinfection: This critical final step eliminates pathogenic bacteria and microorganisms to prevent waterborne
diseases. Common chemical methods include chlorination, ozonization, and UV treatment.

Q4. Explain the disinfection of water by chlorination. Discuss the concept of breakpoint
chlorination with a neat diagram.

Disinfection by Chlorination: Chlorine kills bacteria by acting as a powerful oxidizing agent. When chlorine gas
(Cl2) or hypochlorites are added to water, they react to produce hypochlorous acid (HOCl), which diffuses easily
through bacterial cell walls and deactivates their vital metabolic enzymes:

Cl2 + H2O → HOCl + HCl

HOCl → H+ + OCl- (Hypochlorite ion)

Breakpoint Chlorination: Breakpoint chlorination is a systematic process where sufficient chlorine is added to a
water supply to satisfy the initial chlorine demand, oxidize all organic matters and ammonia compounds, leaving a
stable residual concentration of free available chlorine for protection against future re-contamination.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 3

 Figure 1: Breakpoint Chlorination Curve
[Graph plotted with Residual Chlorine on Y-axis vs Chlorine Dosage on X-axis
showing 4 distinct phases]
Phase 1: Destruction of residual chlorine by reducing agents (No residual).
Phase 2: Formation of chloro-organic compounds and chloramines (Residual rises).
Phase 3: Destruction of chloramines and organic structures (Residual drops to a
minimum/Breakpoint).
Phase 4: Appearance of Free Available Chlorine (Residual rises linearly).

The process follows a distinct four-stage curve:

• Stage 1: Added chlorine is completely consumed in oxidizing reducing impurities (such as Fe2+, Mn2+, H S).
2
Residual chlorine remains zero.
• Stage 2: Chlorine reacts with ammonia and organic matter to form chloramines and organochlorides. The
residual chlorine concentration rises.
• Stage 3: Added chlorine begins to destructively oxidize the newly formed chloramines, liberating nitrogen gas.
The residual concentration drops continuously until it reaches its minimum turning point, known as the
Breakpoint.
• Stage 4: Beyond the breakpoint, all initial chemical demands are fully satisfied. Any additional chlorine added
stays directly in the water as highly stable "Free Available Residual Chlorine" (HOCl and OCl-).

Q5. Explain the various boiler troubles such as Scales, Sludges, Caustic Embrittlement,
and Boiler Corrosion. Discuss their causes, effects, and preventive measures.

When hard water is evaporated continuously in high-pressure boilers, volatile pure water escapes as steam, leading
to an extreme concentration of dissolved salts. This creates major industrial boiler troubles:

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 4

 Trouble Causes Effects Preventive Measures

Sludge Formation Precipitation of loose, soft, Clogs pipes, reduces Frequent operational
slimy suspended solids like thermal efficiency, blow-down operations;
MgCO3, MgCl2, CaCl2 in interferes with water use of soft water feeds.
colder zones of the boiler. flow.

Scale Formation Deposition of hard, sticky, Extreme fuel wastage due Internal conditioning
highly adherent crystalline to insulating property, treatments (Calgon,
crusts on internal heating dangerous overheating, Phosphate); external
surfaces by CaSO4 (solubility boiler distortion, localized softening before entry.
decreases at high temp) or explosions.
Mg(OH)2.

Caustic High alkaline stress corrosion Brittle micro-cracking at Adding Sodium Sulfate
Embrittlement cracks. Occurs when high boiler joints, rivets, and (Na2SO4), Tannins, or
concentrations of NaOH stress lines, resulting in Lignins to plug the micro-
accumulate in microscopic complete structural fissures.
structural crevices via failure.
hydrolysis of Na2CO3.

Boiler Corrosion Chemical/electrochemical Pitting damage, Deaeration (mechanical/

attack on boiler steel caused by: progressive structural chemical using Hydrazine
(a) Dissolved O2, (b) Dissolved wall thinning, reduced N2H4 or Sodium Sulfite
CO2, or (c) Acidic salts equipment lifespan. Na2SO3).
producing HCl via hydrolysis
(e.g., MgCl2).

Q6. Explain the internal treatment methods for boiler feed water. Discuss Calgon,
Phosphate, and Colloidal conditioning with chemical reactions.

Internal Treatment: This involves adding specific chemicals directly into the boiler to react with residual hard-
water salts, converting them into highly soluble compounds or soft, non-sticky suspended sludges that can be
easily blown out during operation.

1. Calgon Conditioning: Calgon is Sodium Hexametaphosphate, Na [Na (PO ) ]. It reacts with scaling Ca2+
2 4 36
ions to exchange sodium and trap the calcium inside a highly soluble, stable complex, preventing crystalline
scale deposition:

Na2[Na4(PO3)6] + 2Ca2+ → Na2[Ca2(PO3)6] (Soluble Complex) + 4Na+

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 5

 2. Phosphate Conditioning: Used extensively in high-pressure boilers. Sodium phosphate salts are added to
react with calcium ions to form soft, loose precipitates of calcium phosphate which are easily removed via
blow-down. The choice of phosphate controls pH:
◦ Trisodium Phosphate (Na3PO4) - used for acidic water.

◦ Disodium Hydrogen Phosphate (Na2HPO4) - used for weakly alkaline water.

◦ Monodium Dihydrogen Phosphate (NaH2PO4) - used for highly alkaline water.

3CaSO4 + 2Na3PO4 → Ca3(PO4)2 ↓ (Loose Sludge) + 3Na2SO4

3. Colloidal Conditioning: Organic colloidal substances like kerosene, tannin, agar-agar, or gelatins are added to
low-pressure boilers. They coat forming scale-crystals, transforming them into loose, non-sticky, amorphous
components that do not adhere to metal walls.

Q7. Explain the softening of hard water by the ion-exchange process with a neat
diagram. Mention its advantages and limitations.

Principle: This process, also known as the demineralization process, completely eliminates all ions from water
using two columns filled with synthetic organic resins containing active functional groups.

Figure 2: Ion-Exchange Process Layout

[Raw Water Feed] → [Cation Exchange Column (R-H)] → [Anion Exchange Column
(R-OH)] → [Pure Demineralized Water Out]

Process and Reactions:

• Cation Exchange Resin (R-H+): Contains acidic groups like -SO H or -COOH. It exchanges all dissolved
3
2+ 2+ + +
metallic cations (Ca , Mg , Na ) for H ions:

2R-H + Ca2+ → R2Ca + 2H+

• Anion Exchange Resin (R-OH-): Contains basic groups like quaternary ammonium structures. It exchanges

all dissolved anions (Cl-, SO42-) for OH- ions:

R-OH + Cl- → R-Cl + OH-

• The liberated H+ and OH- ions combine to produce pure, neutral water: H+ + OH- → H O.
2

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 6

Regeneration: When exhausted, the Cation column is regenerated using dilute HCl or H2SO4, and the Anion
column using dilute NaOH:

R2Ca + 2HCl → 2R-H + CaCl2

R-Cl + NaOH → R-OH + NaCl

Advantages: Produces highly pure demineralized water (hardness down to 0–2 ppm), suitable for high-pressure
industrial boilers; treats highly acidic or alkaline water effectively.

Limitations: High initial setup cost; requires expensive chemical reagents for regular regeneration; turbid or
muddy water cannot be treated directly as it blocks resin pores.

Q8. Describe the principle and working of Reverse Osmosis (RO) for desalination of
brackish water. Mention its advantages and applications.

Principle: Osmosis is the natural flow of pure solvent from a dilute solution into a concentrated solution across a
semi-permeable membrane. If a hydrostatic pressure greater than the natural osmotic pressure is applied to the
highly concentrated salt-water side, the flow direction is reversed. Pure water is forced to flow from the
concentrated salt solution through the membrane to the pure water side, leaving concentrated salts behind.

Figure 3: Reverse Osmosis (RO) Cell

[Applied Hydrostatic Pressure > Π] applied on [Brackish/Salt Water Compartment]
separated by [Semi-Permeable Cellulose Acetate Membrane] → forces Pure Water
into [Fresh Water Outlet]

Working: Brackish water (water containing high dissolved salt concentrations) is pumped into a high-pressure
chamber fitted with a semi-permeable membrane (typically made of Cellulose Acetate, Polyamide, or
Polysulfone). High mechanical pressure (15–40 kg/cm²) is applied, forcing clean, potable water molecules through
the sub-microscopic pores of the membrane, while dissolved ions and macromolecules are rejected and discharged
as concentrated brine.

Advantages: Removes ionic, organic, and microbial impurities simultaneously; very low energy consumption
compared to thermal distillation; simple to operate with low maintenance turn-around; long-lasting membrane
setups.

Applications: Desalination of seawater and brackish groundwater to produce drinking water; reclamation of
industrial wastewater; domestic water purifiers; water purification for electronics and pharmaceutical
manufacturing.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 7

 UNIT-II: Electrochemistry and Corrosion

Q1. Define electrode potential and standard electrode potential. State the Nernst
equation and explain its significance.

Electrode Potential (E): The electric potential difference developed at the interface between a metal electrode and
its own ionic solution when the metal is dipped into it. It represents the tendency of an electrode to lose electrons
(oxidation potential) or gain electrons (reduction potential).

Standard Electrode Potential (E°): The electrode potential measured under standard experimental conditions: a
temperature of 298 K (25°C), a 1 M concentration of metal ions in solution, and a gas pressure of 1 atmosphere
(for gas electrodes).

Nernst Equation: For a general reduction electrode reaction: Mn+ + ne- → M(s), the Nernst equation gives the
mathematical dependency of electrode potential on temperature and ion concentrations:

E = E° - (RT / nF) ln(1 / [Mn+])

At standard temperature (298 K), substituting R, T, and F yields:
E = E° + (0.0591 / n) log10 [Mn+]

Where: E = Electrode potential, E° = Standard electrode potential, R = Gas constant (8.314 J/mol·K), T =
Absolute temperature (K), F = Faraday's constant (96500 C/mol), n = Number of moles of electrons transferred,
and [Mn+] = Molar concentration of metal ions.

Significance: It allows the calculation of cell EMF and electrode potentials under non-standard conditions, helps
determine the direction of spontaneous redox reactions, and enables the measurement of unknown solution pH and
equilibrium constants.

Q2. Explain the construction and working of a galvanic cell. Derive the expression for
EMF of a cell.

Galvanic Cell (e.g., Daniell Cell): A electrochemical device that converts spontaneous chemical energy directly
into electrical energy via redox pathways.

Construction: It consists of two half-cells: an Anode half-cell (e.g., Zinc rod immersed in 1M ZnSO4) and a
Cathode half-cell (e.g., Copper rod immersed in 1M CuSO4). The two solutions are connected internally via a Salt
Bridge (a U-tube containing an inert electrolyte like KCl in agar-agar gel) to maintain electrical neutrality and
complete the internal circuit without mixing solutions. The electrodes are connected externally through a metallic
wire with a voltmeter.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 8

Working & Cell Reactions:

• At Anode (Oxidation): Zinc atoms lose electrons: Zn(s) → Zn2+(aq) + 2e-

• At Cathode (Reduction): Copper ions gain those electrons: Cu2+(aq) + 2e- → Cu(s)

• Net Cell Reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Derivation of Cell EMF Expression: The total Electromotive Force (EMF) of the cell is the potential difference
between the cathode and anode reduction potentials:

Ecell = Ecathode - Eanode

Applying Nernst equation to both half-cells at 298 K:
Ecell = [E°C + (0.0591/n) log[Cu2+]] - [E°A + (0.0591/n) log[Zn2+]]
Ecell = E°cell + (0.0591 / n) log ([Cathode Ions] / [Anode Ions])

Q3. Describe the construction, working, and applications of the Standard Hydrogen
Electrode (SHE). Why is it called a primary reference electrode?

Primary Reference Electrode: An electrode whose absolute potential is arbitrarily assigned as exactly zero volts
at all temperatures, serving as the baseline reference to measure the potentials of all other individual electrodes.

Construction: It consists of a small rectangular piece of platinum foil coated with finely divided platinum black
(to maximize surface area absorption). It is welded to a platinum wire and sealed into a glass tube. This assembly
is immersed in an acidic solution containing exactly 1 M Hydrogen ion concentration (H+, e.g., 1M HCl). Pure,
dry Hydrogen gas (H2) is continuously bubbled through the solution at a constant pressure of 1 atmosphere
through a side inlet.

Cell Representation: Pt, H2(g, 1 atm) | H+(1 M)

Working: Depending on the nature of the paired electrode, the SHE can act either as an anode or a cathode:

• If acting as Anode (Oxidation): H (g) → 2H+ + 2e-

2
• If acting as Cathode (Reduction): 2H+ + 2e- → H (g)
2

Applications: Used as the primary baseline standard to determine standard reduction potentials (E°) of other
electrodes; used to determine the pH of unknown experimental solutions.

Q4. Explain the determination of pH of an unknown solution using the Standard

Hydrogen Electrode (SHE) and Calomel Electrode.

1. Determination of pH using SHE:

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 9

To find the pH of an unknown solution, a half-cell containing a platinum electrode dipped in the unknown solution
with bubbled H2 gas (1 atm) is coupled with a standard reference electrode like the saturated calomel electrode
(SCE, E = 0.2422 V). Here, SHE acts as the anode.

Cell Assembly: Pt, H2(1 atm) | H+(Unknown) || Saturated Calomel Electrode

According to the Nernst equation for SHE acting as an anode: Eanode = 0.0591 log [H+] = -0.0591 × pH (since

pH = -log[H+]).

Ecell = Ecathode - Eanode

Ecell = Ecalomel - (-0.0591 × pH) = 0.2422 + 0.0591 × pH
pH = (Ecell - 0.2422) / 0.0591

2. Determination of pH using Calomel Electrode:

The Calomel electrode is a secondary reference electrode consisting of a mercury layer covered by a paste of
mercurous chloride (Hg2Cl2, calomel) and immersed in a saturated KCl solution. It is extremely stable. When
combined with a hydrogen indicator electrode immersed in an unknown analyte solution, the cell EMF measured
on the potentiometer directly yields the pH value using the exact same equation framework shown above.

Q5. Discuss the chemical (Dry) theory of corrosion.

Chemical / Dry Corrosion: This refers to the direct chemical attack on metal surfaces by atmospheric gases like
oxygen, halogen gases, sulfur dioxide, or hydrogen sulfide in the complete absence of a liquid moisture phase.

The most prominent form is Oxidation Corrosion, occurring via atmospheric oxygen at elevated temperatures.
When metal is exposed to oxygen, it undergoes oxidation to form metal ions, while oxygen is reduced to oxide
ions, forming an intervening oxide film layer on the metal surface:

2M → 2Mn+ + 2ne- (Oxidation)

nO2 + 4ne- → 2nO2- (Reduction)
Net: 2M + nO2 → 2MOn (Metal Oxide Film)

Nature of the Oxide Film (Pilling-Bedworth Rule): The rate of ongoing corrosion depends completely on the
structural nature of this oxide layer:

• Stable/Protective Film: If the volume of the formed metal oxide layer is equal to or greater than the volume of
the metal consumed (Pilling-Bedworth Ratio ≥ 1), it forms a highly dense, non-porous protective barrier that
stops further oxygen diffusion and ceases corrosion (e.g., Al, Cr, Ni).

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 10

 • Unstable Film: The oxide film decomposes back into metal and oxygen as soon as it forms (e.g., Au, Pt, Ag).
No sustained corrosion occurs.
• Volatile Film: The oxide layer evaporates immediately at operating temperatures, exposing fresh metal
surfaces for continuous, rapid corrosion (e.g., Molybdenum oxide).
• Porous Film: The oxide layer contains micro-pores and channels. Atmospheric oxygen continues to diffuse
through these gaps, leading to deep, non-stop corrosion (e.g., Fe, Na, Ca).

Q6. Discuss the electrochemical (wet) theory of corrosion with suitable examples and
reactions.

Electrochemical / Wet Corrosion: This occurs when a metal surface comes into contact with a conducting liquid
electrolyte, or when two dissimilar metals are joined in a moist environment. It is characterized by the formation
of distinct galvanic micro-cells containing separate anodic and cathodic operational zones.

Mechanism:

1. At Anodic Areas: The metal with lower reduction potential undergoes oxidation, dissolving into the solution
as ions and leaving free electrons behind. Anodic areas are always destroyed by corrosion:

M → Mn+ + ne- (e.g., Fe → Fe2+ + 2e-)

2. At Cathodic Areas: The electrons migrate through the metal body to the cathodic zone, where they are
consumed by the environmental electrolyte. The cathode metal itself is entirely protected from corrosion. The
specific cathodic reaction depends on the pH of the medium:
◦ In Acidic Medium (Hydrogen Evolution Type): 2H+ + 2e- → H ↑
2
◦ In Neutral/Alkaline Medium (Oxygen Absorption Type): O + 2H O + 4e- → 4OH-
2 2

Formation of Rust: The metal ions (Fe2+) and hydroxyl ions (OH-) diffuse toward each other and react to form
ferrous hydroxide, which is further oxidized by dissolved atmospheric oxygen to produce hydrated ferric oxide
(Common Yellow-Red Rust):

Fe2+ + 2OH- → Fe(OH)2

4Fe(OH)2 + O2 + 2H2O → 2[Fe2O3 · xH2O] (Rust)

Q7. Explain the following types of corrosion with neat diagrams: Galvanic, Water-line,
and Pitting corrosion.

1. Galvanic Corrosion: Occurs when two dissimilar metals (e.g., Iron and Copper) are in physical contact in an
electrolyte environment. The metal higher up in the electrochemical series (lower reduction potential, e.g., Fe) acts

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 11

completely as an anode and undergoes rapid corrosion, while the less active metal (higher reduction potential, e.g.,
Cu) acts as a cathode and remains safe.

Figure 4: Galvanic & Water-Line Corrosion

[Galvanic]: Iron Rivet (Anode, Corrodes) joining Copper Plate (Cathode, Protected)
[Water-Line]: Steel Tank filled with Water. [Area deep under water] = Low O2 (Anode,
Corrodes). [Area near meniscus] = High O2 (Cathode, Safe).

2. Water-line Corrosion: A form of differential aeration corrosion that occurs on metal walls of tanks or hulls
partially filled with water. The metal section just below the meniscus line is exposed to high dissolved oxygen
levels and acts as a cathode. The deeper metal sections face low oxygen concentration and act as an anode,
undergoing localized horizontal line corrosion just underneath the water surface.

3. Pitting Corrosion: An extremely localized chemical attack that forms pinholes, cavities, or deep pits on a metal
surface. It is initiated by localized breakdown of a protective oxide surface coating (due to scratches or chloride
ion attacks). The tiny exposed metal spot behaves as a concentrated anode, while the surrounding large coated area
acts as a huge cathode. The large cathode-to-anode area ratio causes rapid, deep penetration at the spot.

Q8. Discuss the factors affecting the rate of corrosion under: Nature of the metal and
Nature of the corroding environment.

A. Nature of the Metal:

• Position in Electrochemical Series: Metals with lower reduction potentials are highly reactive and corrode
rapidly (e.g., Zn, Al) compared to noble metals (e.g., Au, Pt).
• Relative Area of Anode and Cathode: The rate of corrosion is directly proportional to the ratio of the cathode
area to the anode area. If the cathode area is very large compared to a tiny anode, corrosion at the anode is
severe because it must supply electrons to a large area.
• Purity of Metal: Impurities in a metal create micro-galvanic cells on its surface, accelerating localized wet
corrosion. Extremely pure metals are highly corrosion-resistant.

B. Nature of the Corroding Environment:

• Temperature: An increase in temperature accelerates the rate of chemical reactions and ion diffusion,
significantly increasing the corrosion rate.
• pH of Medium: Acidic environments (pH < 7) accelerate corrosion due to rapid hydrogen evolution reactions
at the cathode. Alkaline environments generally retard corrosion.
• Humidity/Moisture: Moisture acts as a solvent and conducting electrolyte medium. The rate of atmospheric
corrosion increases drastically with rising relative humidity.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 12

 Q9. What is cathodic protection? Explain the principle and working of the Sacrificial
Anode and Impressed Current Cathodic Protection methods.

Cathodic Protection: A process that suppresses corrosion by forcing the structural metal object to behave entirely
as a Cathode in an electrochemical circuit, thereby protecting it from metal loss.

1. Sacrificial Anode Method:

The structural metal equipment to be protected (e.g., an underground iron pipeline) is connected externally via a
well-insulated wire to a highly active, easily corrodible sacrificial block of metal with a much lower reduction
potential (such as Magnesium, Zinc, or Aluminum). This active metal acts as a concentrated anode, undergoing
sacrificial corrosion while forcing the structural iron pipeline to become a cathode, keeping it protected. The
sacrificial blocks are replaced periodically.

Figure 5: Sacrificial Anode vs Impressed Current Systems

[Sacrificial]: Underground Steel Pipe ←(wire)→ Buried Magnesium Block (Sacrificed)
[Impressed Current]: Underground Steel Pipe ← (-) DC Source (+) → Buried Inert
Graphite Anode Bed

2. Impressed Current Cathodic Protection Method:

Used for massive installations like buried cross-country trans-pipelines or marine ship hulls. An external Direct
Current (DC) power source is utilized. The structural metal pipeline is permanently connected to the Negative
terminal of the DC source, transforming it into a cathode. The Positive terminal is connected to an inert anode
bed (made of graphite, high-silicon iron, or platinum) buried nearby. The external electrical current neutralizes the
natural corrosion currents, preventing metal dissolution.

Q10. Define corrosion. Explain the causes, effects, and methods used for corrosion
control in engineering applications.

Corrosion: The spontaneous destruction and deterioration of a metal or alloy by unwanted chemical or
electrochemical reactions with its surrounding environment.

Causes: Metals naturally exist in a stable, low-energy combined mineral state (oxides, sulfides). Extractive
metallurgy adds energy to isolate pure metals, placing them in an unstable, high-energy state. Corrosion is the
natural thermodynamic process where metals return to their stable combined form.

Effects: Causes catastrophic structural engineering failures (bridges, aircraft components); leaks in high-pressure
oil pipelines; contamination of chemical plant product batches; significant economic losses and safety hazards.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 13

Engineering Control Methods:

• Proper Design: Avoid contact between dissimilar metals; prevent sharp bends, joints, or stagnant structural
pockets where moisture can pool; maximize the anode-to-cathode surface area ratio.
• Cathodic Protection: Utilize sacrificial anodes or impressed current setups.
• Use of Inhibitors: Add chemicals to the corrosive environment. Anodic inhibitors (chromates) form protective
films on anodes; Cathodic inhibitors (amines) limit cathode reactions.
• Protective Coatings: Apply barrier layers to isolate the metal from the environment, including hot-dip
galvanizing (coating iron with zinc), electroplating, or organic paints.

UNIT-III: Energy Sources

Q1. Classify batteries into primary, secondary, and reserve batteries. Explain each type
with suitable examples.

A battery is an electrochemical device containing one or more cells that converts chemical energy directly into
electrical energy through redox reactions.

1. Primary Batteries (Non-Rechargeable): In these cells, the electrochemical reactions occur irreversibly. Once
the active chemical reactants are completely exhausted, the cell cannot be recharged electrically and must be
discarded. They feature high energy density and long shelf lives.
Examples: Leclanché Dry Cell, Zinc-Carbon cell, Alkaline Battery, Mercury button cell.
2. Secondary Batteries (Rechargeable): In these cells, the internal chemical reactions are highly reversible.
After discharge, passing an external direct electrical current through the battery in the opposite direction
restores the original chemical reactants, allowing the battery to be reused for hundreds of cycles.
Examples: Lead-Acid battery, Nickel-Cadmium (Ni-Cd) cell, Lithium-Ion battery.
3. Reserve Batteries: These are specialized safety/military batteries where a key component (typically the liquid
electrolyte) is stored separately in an isolated compartment. The battery remains completely inactive with zero
self-discharge during long-term storage. When needed, the seal is broken to release the electrolyte, instantly
activating the cell.
Examples: Magnesium-Silver Chloride water-activated battery, Zinc-Silver Oxide battery.

Q2. Describe the construction, working principle, cell reactions, advantages, and
applications of a Zinc-Air battery.

Construction: The Zinc-Air battery is a metal-air breathing battery. The Anode consists of a porous, high-surface-
area Zinc metal powder amalgamated with a gel electrolyte. The Cathode is a specialized gas-diffusion structure
made of porous carbon layered with a catalytic agent (like manganese dioxide) that allows atmospheric oxygen to
enter. The Electrolyte is an aqueous alkaline solution of potassium hydroxide (KOH).

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 14

Working & Cell Reactions (Discharging):

• At Anode (Oxidation): Zinc reacts with hydroxyl ions to form zincate, which decomposes into zinc oxide:

Zn + 2OH- → Zn(OH)2 + 2e-

Zn(OH)2 → ZnO + H2O

• At Cathode (Reduction): Atmospheric oxygen diffusing into the porous carbon is reduced:

O2 + 2H2O + 4e- → 4OH-

• Net Cell Reaction: 2Zn + O2 → 2ZnO (Open circuit Voltage ≈ 1.65 V)

Advantages: High energy density because the cathode reactant (oxygen) does not need to be stored inside the
battery body; lightweight; eco-friendly and inexpensive materials.

Applications: Medical hearing aids; remote telemetry telemetry systems; specialized military communication
gear.

Q3. Explain the construction, working, charging and discharging reactions, advantages,
and applications of a Lithium-Ion battery.

The Lithium-ion battery is a state-of-the-art secondary battery operating on "intercalation" mechanisms, where
lithium ions rock back and forth between two layered host structural matrices.

Construction:

• Anode: Layered graphite carbon matrix containing intercalated Lithium atoms (LixC6).

• Cathode: A transition metal oxide layer structure, typically Lithium Cobalt Oxide (LiCoO2).

• Electrolyte: Non-aqueous organic solvent (like ethylene carbonate) containing dissolved lithium salts (such as
LiPF6).

• Separator: Polypropylene micro-porous membrane preventing internal short-circuits.

Operational Reactions (Rocking-Chair Mechanism):

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 15

 During Discharging:
At Anode: LixC6 → 6C + xLi+ + xe-
At Cathode: Li1-xCoO2 + xLi+ + xe- → LiCoO2

During Charging (Reversal):

At Cathode: LiCoO2 → Li1-xCoO2 + xLi+ + xe-
At Anode: 6C + xLi+ + xe- → LixC6

Advantages: Extremely high cell voltage (3.6–3.7 V); high energy density; zero memory effect; low self-
discharge rate (under 5% per month); lightweight.

Applications: Portable consumer electronics (smartphones, laptops); Electric Vehicles (EVs); renewable energy
grid storage systems.

Q4. Explain the construction, working principle, electrode reactions, advantages, and
applications of a Direct Methanol Fuel Cell (DMFC).

A fuel cell is an electrochemical device that converts chemical energy of a continuously supplied fuel and oxidant
directly into electricity without combustion.

Construction: The DMFC uses liquid methanol (CH3OH) as fuel. It consists of a porous Anode and a porous
Cathode, both embedded with a Pt-Ru catalyst. The two electrodes are separated by a solid Proton Exchange
Membrane (PEM), typically made of Nafion, which allows only H+ ions to pass through.

Working & Electrode Reactions: Liquid methanol mixed with water is continuously pumped into the anode
chamber, while oxygen gas or air is fed into the cathode compartment.

• At Anode (Oxidation): Methanol is oxidized to carbon dioxide, releasing protons and electrons:

CH3OH + H2O → CO2 ↑ + 6H+ + 6e-

• The liberated protons (H+) migrate through the Nafion membrane to the cathode, while electrons flow through
the external circuit.
• At Cathode (Reduction): Oxygen combines with incoming protons and electrons to form water:

(3/2)O2 + 6H+ + 6e- → 3H2O

• Net Overall Reaction: CH3OH + (3/2)O2 → CO2 + 2H2O

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 16

Advantages: Liquid methanol is easy to store and transport compared to hydrogen gas; high energy efficiency;
continuous operation without downtime for recharging; eco-friendly byproducts.

Applications: Power sources for military field equipment; portable electronic back-ups; clean transport fuel cells.

Q5. Differentiate between a battery and a fuel cell. Explain the advantages of fuel cells
over conventional batteries.

Feature Battery Fuel Cell

Storage Stores chemical Does not store reactants; Operation Functions Functions
reactants internally fuel and oxidant are Time only until indefinitely
within its body. supplied continuously internal as long as
from an external tank. chemical external
reactants fuel and
are oxidant
exhausted, feeds are
then stops maintained.
for
disposal or
recharging.

Components Electrodes participate Electrodes act primarily

directly in the reactions as catalytic active
and change surfaces and do not wear
composition. out or change
composition.

By-products Can generate heavy Produces completely

metal toxic wastes (Pb, clean byproducts like
Cd, Hg). water vapor and minimal
carbon dioxide.

Advantages of Fuel Cells over Conventional Batteries:

• No Recharging Downtime: They eliminate hours of plug-in charging; operation continues by refueling the
fuel tank.
• Higher Efficiency: Fuel cells bypass thermal Carnot cycle limits, converting chemical energy directly to
electrical power with efficiencies up to 60-70%.
• Environmental Benefits: Exceptionally quiet, vibration-free, and produce negligible pollution compared to
conventional power generation.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 17

 Q6. Define calorific value. Explain Higher Calorific Value (HCV) and Lower Calorific
Value (LCV). Derive the relation between HCV and LCV.

Calorific Value: The total amount of heat energy liberated by the complete combustion of a unit mass (or unit
volume) of a fuel sample.

• Higher Calorific Value (HCV) / Gross Calorific Value: The total quantity of heat released when a unit
quantity of fuel is completely burned, and the combustion products (specifically water vapor generated from
hydrogen) are allowed to cool down to room temperature (15°C / 60°F), thereby recovering the latent heat of
condensation of the water vapor.
• Lower Calorific Value (LCV) / Net Calorific Value: The net heat energy released when fuel is burned
completely and the gaseous combustion products (water vapor) are allowed to escape into the atmosphere
along with their latent heat, without cooling.

Derivation of Relationship: Let a fuel sample contain H% of hydrogen by mass. During combustion, 1 gram of
Hydrogen reacts to form 9 grams of water vapor:

H2 + 0.5O2 → H2O
(2g of H → 18g of water vapor ⇒ 1g of Hydrogen = 9g of water vapor)

Therefore, mass of water vapor produced per gram of fuel = 9 × (H / 100) = 0.09H grams.

The standard latent heat of condensation of water vapor is approximately 587 cal/g (or kcal/kg). Thus, the latent
heat carried away by water vapor per kg of fuel is 0.09 × H × 587.

LCV = HCV - Latent Heat of Water Vapor

LCV = HCV - (0.09 × H × 587) kcal/kg
LCV = HCV - 52.83 × H kcal/kg

Q7. Explain Dulong’s formula for the determination of calorific value of a fuel. Solve a
suitable numerical problem.

Dulong's Formula: An empirical formula used to calculate the theoretical Gross/Higher Calorific Value (HCV) of
a solid or liquid fuel from its ultimate elemental analysis percentages of Carbon (C), Hydrogen (H), Oxygen (O),
and Sulfur (S). It sums the individual calorific contributions of each combustible element:

HCV = (1 / 100) × [8080 · C + 34500 · (H - O/8) + 2240 · S] kcal/kg

Significance of terms: 8080, 34500, and 2240 are the standard calorific values of pure C, H, and S in kcal/kg
respectively. The term (H - O/8) represents the Available Hydrogen for combustion, accounting for the fact that a

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 18

fraction of hydrogen equivalent to O/8 by mass is already chemically bound with oxygen as water (H2O) within
the fuel matrix and cannot contribute to heat generation.

Numerical Problem Example: A coal sample contains C = 80%, H = 6%, O = 8%, S = 1%. Calculate its HCV
and LCV.

Solution:

• Using Dulong's formula for HCV:

HCV = (1 / 100) × [8080 × 80 + 34500 × (6 - 8/8) + 2240 × 1]
HCV = (1 / 100) × [646400 + 34500 × (5) + 2240]
HCV = (1 / 100) × [646400 + 172500 + 2240] = (1 / 100) × 821140 = 8211.4 kcal/kg
• Calculating LCV:
LCV = HCV - 52.83 × H = 8211.4 - 52.83 × 6 = 8211.4 - 316.98 = 7894.42 kcal/kg

Final Answer: Calculated Gross HCV = 8211.4 kcal/kg, Net LCV = 7894.42 kcal/kg.

Q8. Describe the refining of crude petroleum. Explain the need for cracking and discuss
fixed-bed and moving-bed catalytic cracking.

Refining of Crude Petroleum: Raw crude oil extracted from the ground contains impurities (water, sulfur, saline
salts) and is a complex mixture of hydrocarbons. Refining involves cleaning and separating these hydrocarbons
into useful commercial fractions using Fractional Distillation in a tall fractionating tower based on boiling point
gradients. Key fractions collected from top to bottom include Petroleum Gas (<30°C), Petrol/Gasoline (30-120°C),
Kerosene (180-250°C), Diesel (250-320°C), Heavy Fuel Oil, and Residual Asphalt at the bottom.

Need for Cracking: The natural yield of the highly demanded fraction, Petrol/Gasoline (used in automobiles),
from fractional distillation is only about 20%. To meet global market demand, higher-boiling heavy oil fractions
(like heavy diesel and fuel oils) are subjected to Cracking—the thermal or catalytic breakdown of large, high-
molecular-weight hydrocarbons into smaller, low-boiling hydrocarbons suitable for gasoline:

C10H22 (Heavy Alkane) →Cracking C5H12 (Pentane/Gasoline) + C5H10 (Pentene)

Catalytic Cracking Methods: Done in the presence of synthetic Zeolite Alumino-silicate catalysts at lower
temperatures (450–500°C) and pressures (1-5 atm), producing high-octane gasoline.

1. Fixed-Bed Catalytic Cracking: The heavy oil feedstock vapor is preheated and passed through a vertical
reactor containing a stationary, fixed bed of pelletized catalyst. Cracking occurs inside the reactor. Over time,
the catalyst becomes deactivated by a carbon soot/coke layer, requiring the feed to be diverted to an alternate
reactor while the first is regenerated by burning off the coke with hot air.
2. Moving-Bed (Fluidized-Bed) Catalytic Cracking: The catalyst is finely powdered. When hot oil vapors are
pumped from the bottom, the catalyst powder behaves like a turbulent boiling liquid (fluidized state). This

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 19

 enables rapid, uniform mixing and continuous operation: spent catalyst flows out continuously from the bottom
into a separate regenerator chamber where coke is burned off, and regenerated active catalyst is fed back into
the reactor loop without stopping production.

Q9. Discuss the composition, properties, advantages, and applications of LPG and
CNG. Compare them as alternative fuels.

Liquefied Petroleum Gas (LPG): Composed mainly of easily liquefiable propane, n-butane, and isobutane.
Stored under moderate pressure in steel cylinders as a liquid. It is highly volatile, colorless, and odorless, so traces
of Ethyl Mercaptan (C2H5SH) are added to give it a strong warning smell for leak detection. It has a very high
calorific value (≈ 27,800 kcal/m³).

Compressed Natural Gas (CNG): Composed primarily of Methane gas (85-95%) compressed to ultra-high
pressures (200-250 bar). It is lighter than air, meaning it disperses rapidly upwards if a leak occurs, reducing fire
risks.

Comparative Analysis as Alternative Fuels:

Property LPG CNG

Primary Butane and Propane gas blend. Methane gas (CH4).

Composition

Safety Profile Heavier than air. Settles on the ground if Lighter than air. Rapidly rises and disperses
leaked, posing high local explosion hazards. safely into the atmosphere.

Environmental Burns cleanly but releases slightly more Extremely clean; produces the lowest CO,
Impact carbon emissions than CNG. NOx, and particulate emissions.

Applications Domestic household cooking fuel Public mass transport vehicles (buses, auto-
(cylinders); select dual-fuel cars. rickshaws, green cars).

Q10. Explain the Fischer–Tropsch process for the production of synthetic petrol.
Discuss the importance and applications of Hythane and Green Hydrogen.

Fischer-Tropsch (FT) Process: A chemical synthesis method used to manufacture synthetic liquid hydrocarbons
(petrol/gasoline) from coal or natural gas. Coal is first reacted with steam to produce Water Gas (CO + H2). This
syngas mixture is purified to remove sulfur impurities, mixed with extra hydrogen, and passed through a catalytic
reactor at 200–300°C and 10–30 atmospheres over an Iron or Cobalt catalyst. This builds straight-chain liquid
alkanes:

nCO + (2n+1)H2 → CnH2n+2 (Synthetic Alkanes) + nH2O

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 20

The resulting liquid mixture is fractionally distilled to collect high-purity synthetic petrol.

Hythane: Hythane is a specialized alternative fuel mixture containing 10–20% Hydrogen gas blended into
Compressed Natural Gas (CNG).
Importance & Applications: Adding hydrogen broadens the flammability limits of methane, ensuring complete
combustion. This reduces greenhouse emissions of unburnt hydrocarbons and deadly carbon monoxide (CO) by up
to 50% in standard public internal combustion transit engines.

Green Hydrogen: Hydrogen gas produced via the electrolysis of water utilizing 100% clean, renewable energy
sources like solar or wind power, resulting in zero net carbon footprint.
Importance & Applications: It is considered the ultimate clean fuel of the future because its only combustion
byproduct is water vapor (2H2 + O2 → 2H2O). It is applied in clean zero-emission fuel-cell electric vehicles,
rocket propulsion systems, and as a reducing agent in green steel manufacturing plants.

UNIT-IV: Polymers

Q1. Define polymers. Classify polymers based on origin and tactility with suitable
examples.

Polymers: High-molecular-weight macromolecules built by linking together thousands of small, repeating

structural units called Monomers through strong covalent chemical bonds. The process of converting monomers
into polymers is called polymerization.

Classification Based on Origin:

• Natural Polymers: Polymers found in nature, within plants and animals. Examples: Cellulose, Starch,
Proteins, Natural Rubber.
• Synthetic Polymers: Man-made polymers synthesized completely in industrial laboratories from
petrochemical raw elements. Examples: PVC, Polyethylene, Nylon-6,6, Bakelite.
• Semi-Synthetic Polymers: Natural polymers that undergo chemical modifications to improve their mechanical
properties. Examples: Cellulose Nitrate, Vulcanized Rubber.

Classification Based on Tactility (Stereochemistry / Spatial Arrangement): Tactility refers to the spatial
orientation of functional side-groups along the primary carbon-carbon polymer backbone chain:

• Isotactic Polymers: All functional side groups (-R) are arranged uniformly on the exact same side of the main
carbon chain. They are highly crystalline and stable. (e.g., Isotactic Polypropylene).
• Syndiotactic Polymers: Functional side groups alternate positions regularly from one side of the main chain to
the opposite side at every successive monomer step. (e.g., Syndiotactic PVC).
• Atactic Polymers: Functional side groups are arranged in a completely random manner along the chain. They
are amorphous and soft. (e.g., Atactic Polystyrene).

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 21

 Q2. Explain the free-radical addition polymerization mechanism. Discuss the
preparation of Polyvinyl Chloride (PVC) with suitable reactions.

Addition (Chain-Growth) Polymerization: Monomers containing unsaturated double or triple bonds link
together sequentially without the elimination of any small molecular byproducts. The reaction occurs via free
radicals and proceeds in three steps:

1. Chain Initiation: An organic peroxide initiator (like benzoyl peroxide, R-O-O-R) undergoes homolytic
cleavage under heat or light to generate active free radicals (R-O•), which attack a monomer molecule to start
the chain:

R-O-O-R → 2R-O•
R-O• + CH2=CHX → R-O-CH2-CHX•

2. Chain Propagation: The newly formed radical continuously attacks successive monomer molecules, growing
the chain rapidly:

R-O-CH2-CHX• + n(CH2=CHX) → R-O-(CH2-CHX)n-CH2-CHX•

3. Chain Termination: Two growing radical chains couple together or undergo disproportionation to form a
stable, final polymer molecule:

2 R-O-(CH2-CHX)n• → Combined Stable Polymer Chain

Preparation of Polyvinyl Chloride (PVC): Manufactured by the addition polymerization of Vinyl Chloride
monomers under pressure in the presence of a hydrogen peroxide initiator:

n [CH2=CH-Cl] (Vinyl Chloride) →Peroxide / Δ [-CH2-CH(Cl)-]n (PVC)

Applications: Used for electrical insulation coatings, water pipes, raincoats, and medical blood bags.

Q3. Explain condensation polymerization with a suitable example. Describe the

preparation of Nylon-6,6 with chemical equations.

Condensation (Step-Growth) Polymerization: A reaction where bi-functional or poly-functional monomers react

together link-by-link. Each step is accompanied by the elimination of small molecular byproducts such as water
(H2O), ammonia (NH3), or alcohol (HCl). The polymer chain grows slowly step-by-step.

Preparation of Nylon-6,6: Nylon-6,6 is a prominent synthetic polyamide fiber produced by the condensation
polymerization of equal molar ratios of Hexamethylene Diamine (containing 6 carbon atoms) and Adipic Acid
(containing 6 carbon atoms) at elevated temperatures around 250°C under pressure:

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 22

 n [NH2-(CH2)6-NH2] + n [HOOC-(CH2)4-COOH]
↓ High Temp (-2n H2O)
[-NH-(CH2)6-NH-CO-(CH2)4-CO-]n (Nylon-6,6)

During this reaction, the carboxylic acid group (-COOH) of adipic acid reacts with the amine group (-NH2) of
hexamethylene diamine, eliminating a water molecule and creating a strong, recurring amide linkage (-NH-CO-).

Properties & Applications: Features exceptional tensile strength, resistance to abrasion, and elasticity. Used to
manufacture climbing ropes, industrial conveyor belts, toothbrush bristles, and textiles.

Q4. Differentiate between thermoplastics and thermosetting plastics. Give suitable

examples and applications of each.

Property Thermoplastics Thermosetting Plastics

Structure Linear or branched long-chain structures Three-dimensional cross-linked network

with weak intermolecular Van der Waals structures linked by strong covalent
forces. chemical bonds.

Effect of Heat Soften easily on heating and harden upon Do not soften on heating; instead, they
cooling. This cycle can be repeated undergo permanent chemical cross-linking
indefinitely. and harden irreversibly. They burn/char
upon overheating.

Recyclability Can be remelted, remolded, and recycled Cannot be remolded or recycled once cured.
multiple times.

Solubility & Soluble in selective organic solvents; soft Insoluble in all organic solvents;
Mechanicals and flexible. exceptionally hard, brittle, and heat-
resistant.

Examples & Uses Polyethylene, PVC, Polystyrene. Bakelite, Urea-Formaldehyde, Epoxy

Uses: Bottles, pipes, packaging films. Resins.
Uses: Electrical switches, saucepan
handles, circuit boards.

Q5. Define plastics, elastomers, fibers, and rubber. Discuss their important applications
in engineering and daily life.

• Plastics: Linear or cross-linked polymers that can be molded into desired shapes under heat and pressure,
retaining that shape permanently upon cooling.
Applications: Structural gear casings, automobile dashboards, water storage tanks, insulation conduits.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 23

 • Elastomers: High-molecular-weight polymers that possess high elasticity. They can be stretched to several
times their original length under external force and instantly return to their original shape when the force is
released due to loose cross-links.
Applications: Industrial shock-absorbers, gaskets, elastic bands.
• Fibers: Polymeric materials characterized by long, thin, thread-like structures with high tensile strength along
their axis. They feature strong intermolecular hydrogen bonding or dipole-dipole interactions.
Applications: Textiles, bulletproof vests (Kevlar), parachutes, fishing nets.
• Rubber: High-molecular-weight natural or synthetic elastic polymer. Raw natural rubber is tacky and soft, but
can be vulcanized with sulfur to improve its mechanical properties.
Applications: Heavy-duty automobile tires, conveyor belts, shoe soles, surgical gloves.

Q6. Explain the preparation, properties, and applications of Buna-S rubber.

Buna-S Rubber (Styrene-Butadiene Rubber / SBR): A synthetic copolymer rubber produced by the emulsion
copolymerization of 75% 1,3-Butadiene and 25% Styrene in the presence of a sodium catalyst (hence the name:
Bu = Butadiene, Na = Sodium, S = Styrene).

Preparation Reaction:

n [CH2=CH-CH=CH2] (1,3-Butadiene) + m [CH2=CH(C6H5)] (Styrene)

↓ Copolymerization / Na
[-CH2-CH=CH-CH2-]n-[-CH2-CH(C6H5)-]m (Buna-S)

Properties: It possesses high abrasion resistance, excellent load-bearing capacity, good mechanical aging stability,
and resists oxidation better than natural rubber. It requires vulcanization with sulfur to develop high tensile
strength and resilience.

Applications: Primarily used to manufacture heavy-duty automotive tires, vehicle conveyor belts, shoe soles,
rubber gaskets, and wire insulation coverings.

Q7. What are Fiber Reinforced Plastics (FRP)? Explain their composition, properties,
advantages, and engineering applications.

Fiber Reinforced Plastics (FRP): High-performance composite materials consisting of a plastic polymer matrix
reinforced with high-strength structural fibers.

Composition:

• Matrix Phase (Continuous): Thermosetting plastics (like epoxy, polyester, or phenolic resins) or
thermoplastics that bind the fibers together and protect them from environmental damage.
• Fiber Phase (Discontinuous/Reinforcement): High-strength fibers such as Glass fibers, Carbon fibers,
Aramid (Kevlar) fibers, or Boron fibers, which provide tensile strength and rigidity.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 24

Properties and Advantages: Exceptionally high strength-to-weight ratio (stronger than steel yet much lighter);
complete resistance to electrochemical corrosion and chemicals; low thermal conductivity; outstanding fatigue and
impact resistance.

Engineering Applications: Aerospace components (airplane wings, fuselage sections); automotive body panels;
marine boat hulls; chemical storage tanks; high-end sporting goods (tennis rackets, golf clubs).

Q8. Define conducting polymers. Classify conducting polymers with suitable examples.

Conducting Polymers: Specialized organic polymeric materials containing conjugated double-bond networks that
can conduct electricity, showing electrical conductivities comparable to metals.

Classification:

1. Intrinsically Conducting Polymers (ICPs): Polymers whose backbone structure is fundamentally capable of
electrical conduction due to highly conjugated carbon double bonds:
◦ Conjugated Conducting Polymers: Possess continuous alternating single and double bonds along the
backbone. Examples: trans-polyacetylene, polyaniline, polypyrrole.

2. Extrinsically Conducting Polymers: Blended composite polymer systems where conductivity is achieved by
adding external conductive materials into an insulating polymer matrix:
◦ Conductive Element Filled Polymers: Conventional polymer embedded with carbon black, metal flakes,
or copper wires.
◦ Blended Conducting Polymers: Physical blends of a conventional polymer with an intrinsically
conducting polymer.

Q9. Explain the mechanism of electrical conduction in trans-polyacetylene. Discuss the

role of doping in enhancing conductivity.

Conduction Mechanism in trans-polyacetylene: trans-polyacetylene is the simplest prototype conjugated

conducting polymer, featuring alternating carbon-carbon single and double bonds (-CH=CH-CH=CH-). Each
carbon atom is sp2 hybridized, leaving one unhybridized pz orbital perpendicular to the chain. These unhybridized
orbitals overlap along the chain, creating a delocalized π-electron cloud.

In its pure state, the energy gap between the valence band (π band) and conduction band (π* band) is too wide,
making it a semiconductor. Conduction occurs when structural defects called solitons (neutral radical states,
positive carbocations, or negative carbanions) move along the conjugated chain under an applied electric field,
transporting electrical charges.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 25

Role of Doping: Pure trans-polyacetylene has low conductivity. Doping involves adding small amounts of
oxidizing or reducing agents to increase its conductivity by orders of magnitude:

• p-Doping (Oxidative): The polymer is treated with an oxidizing agent like Iodine (I2) or AsF5. This removes
an electron from the polymer chain, creating a positive hole (soliton/polaron) that moves freely, allowing
electrical conduction.
• n-Doping (Reductive): The polymer is treated with a reducing agent like Sodium metal or Lithium. This
injects extra electrons into the empty conduction band, creating negative charge carriers that facilitate electrical
conduction.

Q10. Define biodegradable polymers. Discuss the synthesis, characteristics,

advantages, and applications of Polylactic Acid (PLA).

Biodegradable Polymers: Specialized polymers that can be broken down naturally into eco-friendly, non-toxic
products (like water, carbon dioxide, and biomass) by the action of microorganisms (bacteria, fungi) within a
reasonable timeframe, preventing environmental accumulation.

Polylactic Acid (PLA): A leading biodegradable thermoplastic polyester derived from 100% renewable
agricultural resources like corn starch or sugarcane.

Synthesis: Produced primarily through the Ring-Opening Polymerization (ROP) of a cyclic lactide dimer using
a catalyst (like stannous octoate) under vacuum, or via the direct condensation polymerization of lactic acid
monomers:

n [Lactic Acid] → [-O-CH(CH3)-CO-]n (PLA) + nH2O

Characteristics & Advantages: 100% compostable and bio-absorbable; requires significantly less fossil energy to
manufacture compared to petroleum plastics; releases zero toxic chemical residues upon degradation; highly rigid
with good clarity.

Applications: 3D printing filaments; single-use eco-friendly cutlery and food packaging; agricultural mulch films;
medical bio-absorbable surgical sutures, bone fixation screws, and targeted drug-delivery matrices.

UNIT-V: Advanced Functional Materials

Q1. Define smart materials. Classify smart materials with suitable examples. Discuss
their importance in modern engineering applications.

Smart Materials: Advanced functional materials that can sense external environmental stimuli (such as
temperature, stress, electric fields, magnetic fields, light, or pH changes) and respond by altering their intrinsic
physical properties (like shape, color, viscosity, or electrical conductivity) in a predictable and controlled manner.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 26

Classification and Examples:

• Shape Memory Alloys (SMAs): Metals that return to their original pre-deformed shape upon heating (e.g.,
Nitinol - Ni-Ti alloy).
• Piezoelectric Materials: Generate an electric voltage when mechanical stress is applied, and vice-versa (e.g.,
Quartz, Lead Zirconate Titanate - PZT).
• Chromogenic Materials: Change color in response to environmental inputs: Thermochromic (response to
temperature), Photochromic (response to light).
• Magnetorheological (MR) Fluids: Fluids that change from a liquid to a near-solid state instantly under an
applied magnetic field, altering their viscosity.

Importance in Modern Engineering: They enable the development of adaptive "smart structures" capable of
self-monitoring and real-time adjustment. Used in automated aerospace morphing wings, seismic vibration
dampers in skyscrapers, micro-robotics, and minimally invasive medical surgical tools.

Q2. What are Shape Memory Alloys (SMAs)? Explain the shape memory effect in Nitinol
and discuss its engineering and biomedical applications.

Shape Memory Alloys (SMAs): Specialized metallic alloys capable of remembering their original shape,
returning to it even after undergoing severe mechanical deformation when exposed to an appropriate thermal
stimulus.

Mechanism in Nitinol (Nickel-Titanium Alloy): The shape memory effect relies on a reversible, diffusionless
solid-state phase transformation between two distinct crystal lattice structures:

1. Martensite Phase: The low-temperature phase. It is structurally soft, highly ductile, and easily deformed by
applying external mechanical force.
2. Austenite Phase: The high-temperature phase. It possesses a highly rigid, symmetric cubic crystal structure
that defines the alloy's "parent/memorized shape".

When Nitinol is in its soft Martensite state at room temperature, it can be bent into arbitrary shapes. Upon heating
above a specific transition temperature, its crystal lattice transforms into the rigid Austenite phase, causing the
component to return to its original memorized shape with high force.

Engineering Applications: Self-deploying satellite antennas; temperature-controlled safety valves; aerospace

coupling joints; actuator wires in micro-robotics.

Biomedical Applications: Self-expanding cardiovascular stents (expand inside arteries at body temperature);
orthodontic dental archwires (exert continuous gentle corrective force); orthopedic bone plates.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 27

 Q3. Define piezoelectric materials. Explain the working principle of quartz as a
piezoelectric material and discuss its engineering applications.

Piezoelectric Materials: Materials that interconvert mechanical energy and electrical energy due to their non-
centrosymmetric crystal structures.

Working Principle of Quartz (SiO2): Quartz crystals lack a center of inversion symmetry. In its quiet,

undisturbed state, the centers of positive charges (Silicon ions, Si4+) and negative charges (Oxygen ions, O2-)
coincide exactly, maintaining net electrical neutrality across the crystal faces.

• Direct Piezoelectric Effect: When an external mechanical compressive or tensile force is applied to the quartz
crystal, its lattice deforms. This shifts the centers of positive and negative charges away from each other,
generating a measurable electric voltage across opposite crystal faces.
• Inverse Piezoelectric Effect: Conversely, if an external alternating electrical voltage is applied across the
quartz crystal faces, the ions mechanically shift and displace, causing the crystal to physically expand, contract,
or vibrate at high frequencies.

Engineering Applications: Quartz crystal oscillators for precise timekeeping in digital watches, microprocessors,
and computers; piezoelectric sensors in automotive airbags; sonar underwater transducers; ultrasonic medical
imaging probes.

Q4. Define lubricants. Explain the characteristics of a good lubricant and discuss the
functions of lubricants in engineering systems.

Lubricants: Any substance (liquid, semi-solid, or solid) introduced between two moving or sliding engineering
surfaces to minimize friction, wear, and heat generation.

Characteristics of a Good Lubricant: Optimal viscosity that matches the operational load; high viscosity index
(minimal viscosity changes with temperature fluctuations); high flash and fire points to prevent fire hazards under
heat; excellent chemical and oxidation stability; low cloud and pour points for low-temperature operations; non-
corrosive toward metal surfaces.

Key Functions in Engineering Systems:

• Friction Reduction: Intervenes between surface roughness asperities, replacing high metal-to-metal friction
with low internal fluid shear resistance.
• Wear Minimization: Prevents direct metal-to-metal contact, reducing mechanical abrasion and surface
scoring, which extends equipment lifespans.
• Cooling Medium: Absorbs and carries away frictional heat generated at sliding zones, preventing localized
thermal seizing.
• Corrosion Prevention: Forms a continuous protective barrier layer that shields machined metal surfaces from
moisture and atmospheric oxygen.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 28

 • Sealing and Cleaning: Seals cylinder-piston clearances to prevent high-pressure gas leaks, while sweeping
away abrasive metal debris and carbon deposits.

Q5. Explain the thin film (hydrodynamic) mechanism of lubrication with a neat diagram.
Mention its advantages and limitations.

Thin Film / Hydrodynamic Lubrication: Occurs in high-speed, low-load operating machine components (such
as shafts in journal bearings). A generous amount of liquid lubricant is supplied between the moving parts.

Figure 6: Hydrodynamic Lubrication Profile

[Rotating High-Speed Journal Shaft] completely floating on a thick, continuous fluid
layer of [Liquid Lubricant Film] ⇒ completely separating it from the surrounding
[Stationary Bearing Wall].

Mechanism: When the shaft rotates at high speeds, it drags liquid lubricant into the clearance zone, creating a
dynamic, high-pressure fluid wedge. This hydrodynamic pressure lifts the shaft, allowing it to float completely on
a continuous liquid layer (typically 1000 Å thick). This completely separates the moving metal surfaces, replacing
solid friction with low internal fluid viscosity shear.

Advantages: Minimizes friction and wear because there is no direct metal-to-metal contact; provides excellent
cooling and heat dissipation; drastically extends the operational lifespan of high-speed industrial machinery.

Limitations: Fails completely under high structural operational loads or very low starting speeds, as the
hydrodynamic fluid wedge cannot form, leading to boundary contact; depends entirely on maintaining stable fluid
viscosity.

Q6. Discuss the properties of lubricants and their significance: Viscosity, Cloud Point,
Pour Point, Flash Point, and Fire Point.

1. Viscosity & Viscosity Index: Viscosity is the measure of a fluid's internal resistance to flow.
Significance: It is the single most critical property governing load-bearing capacity. If viscosity is too low, the
oil film squeezes out under pressure; if too high, it causes excessive fluid friction drag. The Viscosity Index
(VI) measures how viscosity changes with temperature; a high VI is preferred because it indicates the lubricant
maintains a stable viscosity across temperature fluctuations.
2. Cloud Point and Pour Point: When a lubricant oil is cooled slowly, the temperature at which it becomes hazy
or cloudy due to the crystallization of paraffin wax is the Cloud Point. Cooling further leads to the Pour Point
—the lowest temperature at which the oil retains its fluid mobility and can still flow.
Significance: These properties dictate the lowest operational temperature limit for machinery working in cold
climates or arctic zones, preventing oil line freezing.
3. Flash Point and Fire Point: The Flash Point is the lowest temperature at which a lubricant oil emits sufficient
flammable vapors to produce a momentary flash of flame when an external test flame is applied. The Fire

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 29

 Point is the higher temperature at which the oil emits enough vapors to catch fire and burn continuously for at
least 5 seconds.
Significance: These are critical safety parameters for high-temperature operations, indicating fire hazards and
explosive limits. A good lubricant must have flash points well above its maximum operating temperature.

Q7. Explain the principle of UV–Visible spectroscopy. Discuss its application in the
analysis of pollutants in the dye industry.

Principle: UV-Visible spectroscopy is an absorption method operating in the wavelength range of 200–800 nm
(UV: 200–400 nm, Visible: 400–800 nm). When a sample molecule absorbs a photon of UV-Vis light, valence
electrons in bonding (σ, π) or non-bonding (n) molecular orbitals are excited to higher-energy anti-bonding empty
orbitals (σ*, π*).

The absorption intensity depends directly on the concentration of the absorbing substance, governed by the Beer-
Lambert Law:

A = log10(I0 / I) = ε · c · l

Where A = Absorbance, ε = Molar absorptivity coefficient, c = Molar concentration, and l = Path length of the cell.

Application in the Dye Industry: Dye industry effluents contain highly toxic, conjugated aromatic organic
chemical pollutants that exhibit intense absorption bands in the visible spectrum due to chromophore groups. By
measuring the absorbance of wastewater samples at characteristic wavelengths (λmax) and comparing them
against standard calibration lines, environmental engineers can monitor pollutant concentrations, detect unlawful
effluent dumping, and evaluate the real-time efficiency of wastewater decolorization and treatment processes.

Q8. Describe the principle of Infrared (IR) spectroscopy and explain its application in
night-vision security systems.

Principle of IR Spectroscopy: IR spectroscopy utilizes light in the wavelength range of 2.5–15 μm. When a
molecule absorbs infrared radiation, it drives transitions between vibrational energy levels. For a molecule to
absorb IR light, it must undergo a net change in its dipole moment during its natural vibrational motions
(stretching or bending). Every functional group has unique, characteristic absorption frequencies, making the IR
spectrum a distinct "molecular fingerprint" used for structural identification.

Application in Night-Vision Security Systems: All physical bodies at ambient temperatures naturally emit
thermal radiation in the mid-to-long infrared spectrum due to internal molecular thermal vibrations. Night-vision
security cameras utilize specialized focal-plane array sensors (made of materials like Indium Gallium Arsenide or
Microbolometers) that detect this invisible thermal IR radiation emitted by living organisms or warm objects in
pitch darkness. The camera processes these varying infrared intensities into real-time visible images, providing
high-contrast night surveillance without requiring external artificial illumination.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 30

 Q9. Explain the working principle of a Carbon Monoxide (CO) sensor based on Passive
Infrared Detection (PID). Discuss its role in pollution monitoring and vehicle emission
control.

Working Principle: A Passive Infrared (PIR/PID) Carbon Monoxide gas sensor operates on the principle of non-
dispersive infrared (NDIR) absorption spectroscopy. The Carbon Monoxide (CO) molecule possesses a permanent
dipole moment and absorbs infrared light at a characteristic wavelength of exactly 4.67 μm, which corresponds to
its fundamental carbon-oxygen stretching vibration.

The sensor contains an infrared light source at one end of a gas chamber and an optical IR bandpass filter tuned
specifically to 4.67 μm paired with a photodetector at the other end. When ambient air containing CO gas fills the
chamber, the CO molecules absorb a fraction of the incoming 4.67 μm infrared light. The reduction in light
intensity hitting the photodetector is measured; by applying the Beer-Lambert law, the internal processor calculates
the exact concentration of CO gas present in parts per million (ppm).

Role in Pollution Monitoring and Vehicle Emission Control:

• Vehicle On-Board Diagnostics: Installed inside automotive exhaust systems to continuously analyze emission
gases, monitoring the efficiency of catalytic converters in converting lethal CO into safer CO2.

• Industrial and Urban Safety: Deployed at busy traffic intersections, enclosed underground parking facilities,
and chemical factories to provide early warnings of toxic CO gas leaks, protecting public health.

Q10. Explain the principle of Raman spectroscopy. Discuss its application in tumour
detection and other medical diagnostic applications.

Principle of Raman Spectroscopy: Based on the inelastic scattering of monochromatic light (typically from a
high-intensity laser) when it collides with molecules. When light hits a sample, the vast majority of photons scatter
elastically with no change in energy, known as Rayleigh scattering.

However, a tiny fraction of photons (1 in every 107) exchange energy with the sample's molecular vibrational
states, scattering inelastically with a change in frequency. This frequency shift is known as the Raman Shift:

Δν = νincident - νscattered

If the scattered photon has lower energy, it creates Stokes lines; if it gains energy from an excited molecule, it
creates Anti-Stokes lines. For a molecule to be Raman active, the collision must cause a temporary change in its
molecular polarizability cloud.

Application in Tumour Detection and Medical Diagnostics: Healthy tissues and cancerous tumour tissues have
distinct biochemical profiles, with different concentrations of proteins, lipids, nucleic acids, and water. When a
laser probe scans a tissue area, it captures real-time, high-resolution Raman spectra. Tumour cells display different
vibrational spectral footprints (such as altered nucleic acid or amide band intensities) compared to healthy cells.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 31

This non-invasive technique allows for real-time, label-free identification of micro-tumour margins during
surgeries and assists in automated biopsy screening for early-stage skin, breast, and gastrointestinal cancers.

Guru Nanak Institute of Technology • Engineering Chemistry (R25) 32