MODULE 1: Periodic Properties & Bonding
1. First ionization energy of Al is less than Mg but reverse is true for second
ionization energy of Al. Explain.
• Answer:
o 1st IE: Magnesium (Mg) has a stable fully filled electronic configuration
(3s2), making it difficult to remove an electron. Aluminum (Al) has a
configuration of 3s2 3p1; the 3p electron is further from the nucleus and
shielded by the s-electrons, making it easier to remove. Therefore,
IE1(Al) < IE2(Mg).
o 2nd IE: After losing one electron, Mg becomes Mg+ (3s1) and Al
becomes Al+ (3s2). Now, Al^+ has the stable fully filled s-orbital,
while Mg^+ has an unpaired electron that is easier to remove.
Therefore, IE2(Al) > IE2(Mg).
2. From each set, predict which one has lower first ionization enthalpy? Justify
your answer.
• (i) N or O: Oxygen (O) has lower ionization energy. Nitrogen has a stable
half-filled p-orbital (2p3), whereas Oxygen (2p4) has electron-electron
repulsion in one of the p-orbitals, making it easier to remove that electron.
• (ii) I or I⁻: I⁻ has lower ionization energy because it has an extra electron,
increasing electron-electron repulsion and effective shielding, making the
outer electron easier to remove.
• (iii) Mg, P or Ar: Mg. Argon is a noble gas (highest IE), Phosphorus is half-
filled (high IE). Magnesium is a metal and naturally electropositive, giving up
electrons more easily than the non-metals P and Ar.
• (iv) Na or Na⁺: Na. Na⁺ has a stable noble gas configuration (Neon
configuration), making it extremely hard to remove an electron. Na is an alkali
metal willing to lose an electron.
3. Give the values of the quantum numbers for electron with the highest
energy in sodium atom.
• Answer: Sodium (Na, Z=11) configuration is 1s2 2s2 2p6 3s1. The highest
energy electron is in 3s.
o Principal quantum number (n) = 3
o Azimuthal quantum number (l) = 0 (s-orbital)
o Magnetic quantum number (ml) = 0
o Spin quantum number (ms) = +1/2 or -1/2
4. Define electron affinity (EA) and electronegativity. Compare the electron
affinity and electronegativity of F and Cl.
• Definitions:
o Electron Affinity: The energy change that occurs when an electron is added
to a neutral gaseous atom to form a negative ion.
o Electronegativity: The tendency of an atom in a molecule to attract the
shared pair of electrons towards itself.
• Comparison:
o Electronegativity: F > Cl. Fluorine is the most electronegative element due to
its small size.
o Electron Affinity: Cl > F. Although F is more electronegative, its very small
size creates high electron density, causing repulsion for the incoming electron.
Chlorine has a larger volume to accommodate the extra electron more easily.
5. Describe Fajan’s rule.
• Answer: Fajan’s rule predicts the covalent character in ionic bonds. A bond
has more covalent character if:
1. The cation is small (high polarizing power).
2. The anion is large (high polarizability).
3. The cation has a high charge.
4. The cation has a "pseudo-noble gas" configuration (18 valence
electrons).
6. Briefly explain the general characteristic of s, p, d and f block elements.
• s-block: Soft metals, low ionization energy, highly reactive, form ionic
compounds (except Li/Be).
• p-block: Contains metals, non-metals, and metalloids; variable oxidation
states; form covalent and ionic compounds.
• d-block (Transition metals): High melting points, variable oxidation states,
form colored ions and complexes, act as catalysts.
• f-block (Inner transition): Heavy metals, lanthanides (rare earths) and
actinides (radioactive), similar chemical properties within series.
7. Discuss the physical properties trends in the group trends and periodic
trends in the Periodic table.
• Atomic Radius: Decreases across a period (left to right); Increases down a
group.
• Ionization Energy: Increases across a period; Decreases down a group.
• Electronegativity: Increases across a period; Decreases down a group.
• Metallic Character: Decreases across a period; Increases down a group.
8. Discuss the Valence Bond Theory and hybridizations.
• Valence Bond Theory (VBT): States that covalent bonds form when half-
filled atomic orbitals of two atoms overlap. The greater the overlap, the
stronger the bond. It distinguishes between Sigma (\sigma) bonds (head-on
overlap) and Pi (\pi) bonds (sideways overlap).
• Hybridization: The intermixing of atomic orbitals of slightly different energies to
form new sets of equivalent orbitals (e.g., sp, sp2, sp3) to minimize repulsion
and explain molecular geometry.
9. Write short notes on Bond moment, dipole moment and electro negativity
differences.
• Bond Moment: The polarity of an individual bond caused by electronegativity
differences.
• Dipole Moment (mu): The vector sum of all individual bond moments in a
molecule. If the geometry is symmetrical (like CO2 or CCl4), the dipole
moment may be zero even if bonds are polar.
• Electronegativity Difference: Determines bond type. Large difference (>1.7)
= Ionic; Small difference (0.4–1.7) = Polar Covalent; Negligible difference
(<0.4) = Non-polar Covalent.
MODULE 2: Structure & Bonding
1. Compare the bond angles in NH3 and NF3 on the basis of VSEPR theory.
• Answer: Both are pyramidal (sp3 with 1 lone pair).
o NH3 (107°): The bond pairs are attracted to N. The repulsion between
the bond pairs is high, opening the angle.
o NF3 (102°): Fluorine is highly electronegative, pulling electrons away
from N. The bond pairs are closer to F, reducing the repulsion between
bond pairs near the Nitrogen, allowing the lone pair to push them
closer together, resulting in a smaller angle.
2. Predict the shapes of BrF3 and BrF5 on the basis of VSEPR theory.
• BrF3: 7 valence electrons (Br) + 3 bonded = 10 electrons à 5 pairs (3 BP, 2
LP). Structure: Trigonal Bipyramidal arrangement. Shape: Bent T-shaped.
• BrF5: 7 valence electrons (Br) + 5 bonded = 12 electrons à 6 pairs (5 BP, 1
LP). Structure: Octahedral arrangement. Shape: Square Pyramidal.
3. Explain the concept of hybridization using NH3 and PF5 as examples.
• NH3: Nitrogen (2s2 2p3) undergoes sp3 hybridization. 3 hybrid orbitals form
bonds with H, 1 holds a lone pair. Shape: Pyramidal.
• PF5: Phosphorus (3s2 3p3) excites a 3s electron to a 3d orbital. It
undergoes sp3d hybridization to form 5 equivalent bonds. Shape: Trigonal
Bipyramidal.
4. Predict the shape and Hybridization of the following molecules:
• NH4+: sp3, Tetrahedral.
• C2H2: sp, Linear.
• PCl5: sp3d, Trigonal Bipyramidal.
• SO42-: sp3, Tetrahedral.
• NH3: sp3, Pyramidal.
5. Define electron affinity
o The energy change that occurs when an electron is added to a neutral
gaseous atom to form a negative ion.
6. Write short notes on position of hydrogen and noble gases in the periodic
table.
• Hydrogen: Anomalous position. It resembles Alkali metals (Group 1) by
having ns1 config and losing an electron (H+), but also resembles Halogens
(Group 17) by gaining an electron (H-) and forming diatomic molecules (H2).
Usually placed at the top of Group 1.
• Noble Gases: Placed in Group 18 (Zero Group) because they have fully filled
valence shells (ns2np6), rendering them chemically inert (stable octet).
MODULE 3: Thermodynamics
1. Define entropy and explain its significance in thermodynamics. Predict in
which of the following entropy increases or decreases.
• Definition: Entropy (S) is a thermodynamic quantity representing the
unavailability of a system's thermal energy for conversion into mechanical
work, often interpreted as the degree of disorder or randomness in the
system.
• Significance: The Second Law of Thermodynamics states that the total
entropy of an isolated system can never decrease over time. It determines
spontaneity (ΔG = ΔH - TΔS).
• Predictions:
o A liquid crystallizes into solid: Entropy Decreases (Ordering
increases).
o Temperature of a crystalline solid is raised from 0K to
15K: Entropy Increases (Thermal motion increases).
o 2NaHCO3(s) à Na2CO3(s) + CO2(g) +
H2O(g): Entropy Increases significantly because solids are converting
into gases, which are much more disordered.
MODULE 4: Phase Equilibria
1. In a two-component system with one phase, calculate the number of
degrees of freedom.
• Formula: Gibbs Phase Rule F = C - P + 2
• Calculation: C = 2 (components), P = 1 (phase).
• F = 2 - 1 + 2 = 3.
• Answer: The system is trivariant (Degrees of freedom = 3).
2. State Gibbs Phase Rule and explain the meaning of each term.
• Rule: For a heterogeneous system in equilibrium, F = C - P + 2.
• Terms:
o P (Phases): Physically distinct, mechanically separable parts of the
system (e.g., solid, liquid).
o C (Components): The minimum number of independent chemical
constituents required to define the composition of all phases.
o F (Degrees of Freedom): The number of intensive variables (Temp,
Pressure, Conc) that can be varied independently without changing the
number of phases.
3. For the ice-water-vapour equilibrium, calculate the degrees of freedom using
the phase rule.
• Context: This is the triple point of water.
• Values: C = 1 (H2O), P = 3 (Solid, Liquid, Gas).
• Calculation: F = 1 - 3 + 2 = 0.
• Answer: Zero degrees of freedom (Invariant). The system exists only at a
specific Temperature and Pressure.
4. Describe the phase diagram of CO2 and mention the significance of the
critical point.
• Description: The CO2 diagram shows regions for Solid (Dry Ice), Liquid, and
Gas. Unlike water, the Solid-Liquid line slopes to the right (melting point
increases with pressure). At 1 atm, CO2 sublimes (goes solid gas) at -
78.5°C. Liquid CO2 exists only above 5.1 atm. * Critical Point: The point at
the end of the liquid-gas boundary. Above this temperature (31.1°C for CO2)
and pressure, the liquid and gas phases become indistinguishable, forming
a supercritical fluid. It cannot be liquefied by pressure alone above this
temperature.
MODULE 5: Reaction Intermediates
1. Differentiate between heterolytic and homolytic bond cleavage. Give
examples.
• Homolytic: Bond breaks evenly. Each atom retains one electron, forming
Free Radicals.
o Example: Cl-Cl + UV Light à Cl• + Cl•
• Heterolytic: Bond breaks unevenly. One atom takes both electrons, forming
Ions (Cation/Anion).
o Example: CH3-Cl àCH3+ + Cl-
2. What are carbenes? Differentiate between singlet and triplet carbenes in
terms of stability.
• Carbenes: Neutral reactive intermediates containing a divalent carbon with 6
valence electrons (:CH2).
• Singlet Carbene: Spins are paired (sp2 hybrid). Less stable in gas phase.
• Triplet Carbene: Spins are parallel (unpaired) in different orbitals (sp hybrid-
like). More stable generally due to Hund's rule (less inter-electronic
repulsion).
3. Explain the concept of hybridization in methane, ethane and ethyne.
• Methane (CH4): sp3 (Tetrahedral).
• Ethane (C2H6): sp3 (Tetrahedral geometry at each carbon).
• Ethyne (C2H2): sp (Linear geometry).
4. Explain the structure and factors affecting the stability of carbanions.
• Structure: Pyramidal (sp3) hybridized with one lone pair).
• Stability Factors:
o Inductive Effect: Electron Withdrawing Groups (-I) stabilize
carbanions by dispersing the negative charge. Electron Donating
Groups (+I) destabilize them.
o Resonance: Delocalization of the negative charge stabilizes the ion
(e.g., Benzyl carbanion).
o s-character: Higher s-character (sp > sp2 > sp3) means the orbital is
closer to the nucleus, stabilizing the negative charge.
5. Arrange the following in increasing order of stability. Justify your answer.
• (i) Carbocations:
o Order: CH3+ < CH3CH2+ < (CH3)2CH+ < (CH3)3C+
o Justification: Alkyl groups are electron-releasing (+I effect) and stabilize
the positive charge. Hyperconjugation also increases with more alpha-
hydrogens (9 in tertiary vs 0 in methyl).
• (ii) Carbanions:
o Order: (CH3)3C- < (CH3)2CH- < CH3CH- < CH3- < C6H5CH2-
o Justification: Alkyl groups (+I) intensify the negative charge,
destabilizing it. Therefore, Tertiary is least stable. The Benzyl
carbanion (C6H5CH2-) is most stable due to Resonance.
• (iii) Free radicals:
o Order: CH3• < CH3CH2• < (CH3)2CH•< (CH3)3C•
o Justification: Follows the same trend as carbocations due to
Hyperconjugation and +I effect stabilizing the electron deficiency.
6. What are the products formed when a covalent bond breaks heterolytically?
Give one example.
• Answer: A Cation (positive ion) and an Anion (negative ion).
• Example: H-Cl àH+ + Cl-
7. How does hyperconjugation and inductive effect contribute to carbocation
stability? Explain.
• Inductive Effect (+I): Alkyl groups push electron density through the sigma
bond toward the positively charged carbon, reducing the charge density and
stabilizing the ion.
• Hyperconjugation: The sigma electrons of an adjacent C-H bond overlap
with the empty p-orbital of the carbocation, delocalizing the positive charge.
More alpha-hydrogens = More hyperconjugation = Higher stability.
MODULE 6: Heterocyclic Compounds
1. What are heterocyclic compounds? Give one example each of a five-
membered and a six-membered heterocycle containing nitrogen atoms.
• Definition: Cyclic organic compounds where at least one atom in the ring is
an element other than carbon (e.g., N, O, S).
• 5-Membered: Pyrrole or Imidazole.
• 6-Membered: Pyridine or Pyrimidine.
2. How does pyrazole differ from imidazole in terms of nitrogen atom
positions?
• Pyrazole: A 5-membered ring with two Nitrogen atoms adjacent to each other
(Positions 1 and 2).
• Imidazole: A 5-membered ring with two Nitrogen atoms separated by one
carbon (Positions 1 and 3).
3. Explain why pyridine is more basic than pyrrole.
• Pyridine: The lone pair on Nitrogen is in an sp2 orbital perpendicular to the pi-
system. It is not involved in aromaticity and is available for donation to a
proton.
• Pyrrole: The lone pair on Nitrogen is in a p-orbital and is part of the aromatic
sextet (delocalized ring current). It is not available for protonation because
doing so would break the aromaticity of the ring.
• Conclusion: Pyridine is a stronger base.
4. What is the difference between pyrrole and pyridine in terms of basicity?
• Pyridine is a moderate base because its lone pair is free. Pyrrole is a very
weak base (essentially non-basic) because its lone pair is delocalized into the
aromatic ring system.