LUMS ID: December 22, 2023

CHEM 101
Principles of Chemistry
Final Exam
Total marks: 90, Time: 120 minutes

Section 1: MCQs: Encircle the correct answer. Please do not overwrite. Overwriting will result in
zero marks. (20  1 = 20 marks)

Q1. The correct increasing order of bond angles in H2S, NH3, BF3, SiH4, and XeF4 is:
a. NH3 < H2S < SiH4 < BF3 < XeF4
b. H2S < SiH4 < NH3 < XeF4 < BF3
c. XeF4 < H2S < NH3 < SiH4 < BF3
d. H2S < XeF4 < NH3 < BF3 < SiH4
Q2. The density of states increases as we approach the:
a. Highest energy side of a band
b. Lowest energy side of a band
c. Middle of the energy range of a band
d. Both a and b

Q3. The position and intensity of the signals in the spectrum obtained in photoelectron spectroscopy
respectively depict:
a. number of electrons and ionization energy
b. number of electrons and electronegativity
c. ionization energy and number of electrons
d. electronegativity and ionization energy

Q4. The width of a band in metals as well as in semiconductors depends on:

a. The number of valence electrons
b. Strength of interaction between the orbitals
c. Physical state of the constituting atoms
d. Bohr’s radius

Q5. Which one of the following molecules exhibits dsp3 hybridization?

a. SF4
b. NH3
c. BrF5
d. SO2
Q6. Pick the correct decreasing order of wavenumber values at which the following bonds will resonate in
IR spectroscopy: C–Cl, C–Br, C–C, C–O, and C–H?
a. C–Cl > C–Br > C–C > C–H > C–O
b. C–O > C–H > C–Br > C–Cl > C–C
c. C–H > C–C > C–O > C–Cl > C–Br
d. C–Br > C–Cl > C–C > C–O > C–H

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Q7. Pick the correct decreasing order of wavenumber (cm-1) for the carbon-carbon single, double and triple
bonds in IR spectroscopy.
a. alkynes > alkenes > alkanes
b. alkanes > alkynes > alkenes
c. alkenes > alkynes > alkanes
d. alkynes > alkanes > alkenes
Q8. Comparing I–Cl (ICl) and Br–Br (Br2) molecular species, the boiling point of ICl is about 40°C higher
than the boiling point of Br2. Pick the correct reason for this observation:
a. Iodine (I) has a larger size than bromine (Br)
b. I-Cl bond is a weaker than Br-Br bond
c. Ionization energy of iodine is lower than the ionization energy of bromine
d. ICl is a polar molecule, while Br2 is a nonpolar molecule
Q9. Among the following molecules: SO2, SF4, ClF3, BrF5, and XeF4, which of the following shapes does
not describe any of the molecules mentioned?
a. Bent
b. See-saw
c. Trigonal planar
d. T-shaped

Q10. In allyl anion, the electron density is greatest:

a. on the central carbon atom
b. on both the end (terminal) carbon atoms
c. all carbon atoms have equal electron density
d. on the first carbon atom only

Q11. The nature of the interaction that keeps diamond and silica in solid form is:
a. electrostatic interaction
b. non-covalent bonding
c. covalent bonding
d. delocalized bonding

Q12. For a semiconductor not exposed to any external energy source:

a. the valence and conduction bands are partially filled to impart semiconducting nature
b. the valence band is partially occupied while the conduction band is completely empty to impart
semiconducting nature
c. the valence band is fully occupied while the conduction band is completely empty to impart
semiconducting nature
d. the valence band is fully occupied while the conduction band is partially filled to impart
semiconducting nature

Q13. The hybrid orbital approach does not provide information about the:
a. Number of lone pairs of electrons in a molecule
b. Magnetic behavior of a molecule
c. Number of -bonds in a molecule
d. Molecular shape

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Q14. Absorption of infrared (IR) radiations by molecules results in:
a. Excitation of electrons from lower energy to higher energy molecular orbitals
b. Excitation of molecules from a lower rotational energy level to a higher rotational energy level
c. Excitation of molecules from a lower vibrational energy level to a higher vibrational energy level
in a given electronic energy level.
d. Excitation of molecules from a vibrational energy level of ground electronic energy level to
another vibrational energy level in the first excited electronic energy level.

Q15.Which of the following compounds should not exist:

a. NF5
b. PF3
c. NF3
d. PF5
Q16. The change in pressure and temperature:
a. can change the physical state of matter but not the electrical conductivity
b. cannot change the physical state of matter but can change the electrical conductivity
c. can change both the physical state and electrical conductivity
d. can change neither the physical state nor the electrical conductivity
Q17. Bonding between valence orbitals of 10,000 Na atoms using the concept of orbitals in a row will
generate crystal orbitals where the 4,000th orbital going from the lower to the highest energy side will
have:
a. 4,000 antibonding interactions
b. 3,999 antibonding interactions
c. 2,000 antibonding interactions
d. 4,001 antibonding interactions
Q18. The backbone, also referred to as main chain, of the addition polymers generally consists of:
a. carbon atoms and ester functionality
b. carbon atom and amide functionality
c. carbon atoms only
d. carbon atom and ether functionality.
Q19. Hyperconjugation allows:
a. orbitals of the central atom of a molecule to undergo hybridization
b. central atom of a molecule to expand its octet
c. molecules to exist in multiple distinct shapes
d. molecules to change their vibrational energies
Q20. Pick the option which remains unchanged for cis and trans isomers of an alkene:
a. Molecular weights
b. Dipole moments
c. Densities
d. Boiling points

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Section 2: True/False. State whether the statements below are true or false. Give a rationale to
support your choice. (5  1 = 5 marks)
1. In bulk state, the band width in metals and width of the valence and conduction bands in
semiconductors and insulators as well as their band gaps are fixed.

2. Reducing the number of atoms constituting a metal sample does not change its metallic nature and
optical properties even if there are only 2 atoms that are bonded together.

3. The dispersion forces are stronger in branched chain hydrocarbons than straight chain hydrocarbons.

4. In photoelectron spectroscopy, the kinetic energy of ejected electrons is measured to determine the
binding energy of electrons in a material.

5. The major resonance contributor of butadiene is the one where charge separation and double bond
character are maximized.

Section 3: Structured questions.

Provide short answers to the following questions. (Total 65 marks)

Q1. Pentacene is a highly conjugated compound. It is an organic semiconductor and is widely explored for
applications in organic electronics. The structures of pentacene, hexacene, and tetracene are given below:
(1+1=2 marks)

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 A. What will happen to the energy gap between the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) in the case the pentacene is converted into
hexacene?

B. What will happen to the energy gap between the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) in the case the pentacene is converted into
tetracene?

Q2. Diamond and graphite are two allotropic forms of carbon. Describe the differences and origin of
differences in the electrical conductivities of diamond and graphite. Also, compare the conductivity
behavior of graphite and lead (Pb). (2 marks)

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Q3. Lewis structures show how the valence electrons are assigned to the atoms constituting a species.

(3 marks)

A. Draw the Lewis structure for SF2 depicting bonding in this system. Include the formal charges on
all atoms.
(1 mark)

B. The dimer of this compound has the formula S2F4, and it has been shown to have F3S-SF structural
arrangement. Draw a possible Lewis structure to represent the bonding in the dimer, indicating the
formal charges on all atoms. Is it possible to draw a Lewis structure for S2F4 in which all atoms
satisfy the octet rule? (2 marks)

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Q4. Nanoparticles are small particles with sizes ranging between 1 to 100 nanometers. Nanoparticles are
used in various applications due to their unique size dependent optical properties. (4 marks)

A. What is the origin of the unique optical properties of gold nanoparticles? Name and describe the
underlying phenomenon responsible for the unique optical properties of gold nanoparticles.
(2 marks)

B. Quantum dots made from the same material can be made to fluoresce and emit light of almost any
color. Using the concepts of bonding, give a rationale to explain this phenomenon. (2 marks)

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Q5. A polymer is a large molecule, also called macromolecule, made by linking repeat units stemming from
small molecules called monomers. Plastics of every kind, tree bark, and even DNA and RNA are polymers.
(8 marks)

A. Describe the key characteristics required for a monomer to undergo: (2 marks)

a) Addition polymerization
b) Condensation polymerization

B. Sketch and label the reaction scheme depicting different steps involved in the addition
polymerization of tetrafluoroethylene (TFE). The structure of TFE is given below. (3 marks)

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 C. The monomer glycine (NH2-CH2-COOH) can undergo condensation polymerization to form
polyglycine. Sketch and label the reaction scheme for the synthesis of polyglycine. (2 marks)

D. The structure of a polymer produced by the addition polymerization is given below:

Draw the structure of the monomer that can be used to synthesize this polymer. (1 mark)

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Q6. Micelles and liposomes are structures formed by the self-assembly of amphiphilic molecules in aqueous
environment. Typically, micelles are made up of a single layer of amphiphilic molecules, while liposomes
are made up of a double layer of amphiphilic molecules. (6 marks)

A. What type of molecules can be encapsulated in the cavity of a liposome: hydrophobic or

hydrophilic? (1 mark)

B. What type of molecules can be encapsulated in the center of a micelle: hydrophobic or hydrophilic?
(1 mark)

C. Rank the following molecules in increasing order of their boiling point. Lowest to highest.
(2 marks)

D. Indicate the hydrophobic and hydrophilic parts of Vitamin A depicted below. Would you expect it
to dissolve in water? (2 marks)

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Q7. The chemical structures of 1,3-pentadiene and 1,4-pentadiene are given below: (5 marks)

A. Why the rotation around the bond between C2 and C3 is restricted in the case of 1,3-pentadiene
while rotation is possible around the bond between C2 and C3 in the case of 1,4 pentadiene?
(2 marks)

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 B. Using the concept of the interaction of orbitals in a row, can you support the observation that both
the C-O bonds in the carboxylate anion are equivalent? Additionally, by drawing the forms of the
π-molecular orbitals, comment on the nature of the π-bonding in the carboxylate anion. (3 marks)

Q8. Hybridization (6 marks)

A. Determine the hybridizations of the central atoms and geometries of the following molecules and
ions: SbF6–, BH4–, CS2, NF2–, SF4, XeO2F2 (3 marks)

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 B. Ammonia (NH3) can act as a base and take up a proton to form ammonium ion (NH 4+). Comment
on the change in hybridization, predict the change in the percentage of s character in the hybrid
orbitals, and predict the new bond angle for NH4+. (3 marks)

Q9. Spectroscopy is the study of the interaction between matter and electromagnetic radiation as a function
of the wavelength or frequency of the radiation. Infrared spectroscopy is a simple and rapid technique that
can give evidence for the presence of various functional groups in a substance. (12 marks)

A. CO2 is a linear molecule. There is no net molecule dipole moment since the individual bond dipole
moments cancel out each other. However, the experimental data shows that CO2 is an IR active
molecule. Give a rationale to explain this observation. (2 marks)

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B. The infrared spectrum of gaseous NaH was determined through IR spectroscopy. A single
absorption band was observed at λ = 8.53 µm (1µm = 1×10-6 m). Calculate the vibrational force
constant of the NaH molecule. The reduced mass (µ) of one NaH molecule in kg unit can be
𝑚1𝑚2
estimated from  = 𝑚1+𝑚2 (atomic mass of Na = 23 g/mole, atomic mass of H = 1 g/mole).
(2 marks)

C. Four pairs of molecules (I-IV) are sketched below. Identify characteristic vibrations that would
give signals in IR spectra and would help in differentiating between the molecules of a given pair.
(8 marks)

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Pair I

Pair II

Pair III

Pair IV

Q10. Both silicon (Si) and germanium (Ge) are semiconductors that are being used in solar cells for
harvesting sunlight and converting it into electrical energy. Their band gaps are 1.11×10−19 J and
0.67×10−19 J, respectively, at room temperature. Calculate the wavelength of light that is capable of exciting
electrons across the band gap in each of these substances. (2 marks)

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Q11. Why lead (Pb) is much better conductor of electricity than germanium (Ge)? Why does conductivity
of a semiconductor materials increase with the increase in temperature? (1+1 = 2 mark)

Q12. Structures of cholesteryl benzoate (used in liquid crystal displays), ciprofloxacin (an antibiotic) and
doxorubicin (an anticancer drug) are given below. (a) Mark the hybridization of all the atoms, except
hydrogen, on the below given structures. (b) Also list on the right side of each structure all the functional
groups that you can identify in them. (c) Keeping in view your answers to the first two parts, describe the
three-dimensional conformation of doxorubicin, especially commenting on the planar and non-planar parts
of this molecule. (9 marks)

Cholesteryl benzoate

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Ciprofloxacin

Doxorubicin

Q13. Draw an MO diagram for oxygen O2 using the hybrid MO approach, considering that the oxygen
atoms are sp3 hybridized. Comment on how the bonding picture presented by your hybrid MO diagram with
sp3 hybridized oxygen atoms relates to the commonly accepted boning and valence electron distribution in
oxygen molecule. (2+2=4 marks)

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 Formula Sheet
Constants:
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 (𝑚𝑒 ) = 9.1 × 10−31 𝑘𝑔

𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 (𝑒) = 1.6 × 10−19 𝐶

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑡𝑜𝑛 = 1.673 × 10−27 𝑘𝑔

𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠
𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜 ′ 𝑠 𝑁𝑢𝑚𝑏𝑒𝑟 = 6.02 × 1023
𝑚𝑜𝑙
𝑃𝑙𝑎𝑛𝑐𝑘 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (ℎ) = 6.626 × 10−34 𝐽. 𝑠
𝑚
𝑆𝑝𝑒𝑒𝑑 𝑜𝑓 𝑙𝑖𝑔ℎ𝑡 (𝑐) = 3 × 108
𝑠
𝑅𝑦𝑑𝑏𝑒𝑟𝑔 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑅𝐻 ) = 2.176 × 10−18 𝐽
𝑒 𝐶
𝑐ℎ𝑎𝑟𝑔𝑒 𝑡𝑜 𝑚𝑎𝑠𝑠 𝑟𝑎𝑡𝑖𝑜 ( ) = −1.76 × 108
𝑚 𝑔
M𝑎𝑠𝑠 𝑜𝑓 𝑛𝑒𝑢𝑡𝑟𝑜𝑛 = 1.675 × 10−27 𝑘𝑔

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑏𝑒𝑡𝑎 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 (β) = 9.11 × 10−31 𝑘𝑔

𝑚𝑎𝑠𝑠 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑎𝑡𝑜𝑚 = 1.674 × 10−27 𝑘𝑔 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑝ℎ𝑎 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 = 6.64 × 10−27 𝑘𝑔

1µm = 1×10-6 m 1A0 = 10-10m, 1 pm= 10-12m a0 = 52.9pm

Equations:
𝑍𝑒𝑓𝑓 2 𝑛2 𝑛2 ℎ 2 1
𝐸 = −𝑅𝐻 𝑟= 𝑎0 𝑟= 𝜈̅ =
𝑛2 𝑍𝑒𝑓𝑓 4𝜋2 𝑚𝑍𝑒 2 𝜆

𝑍2 𝑚𝑒 𝑒 4 𝑍2 ɛ0 ℎ 2
𝐸 = −𝑅𝐻 𝑛2 𝐸=− × 𝑎0 =
8ɛ0 2 ℎ 2 𝑛2 𝑚𝑒 𝜋𝑍𝑒 2

𝑚𝑟𝑒𝑠𝑡 1 𝐾
𝑚𝑟𝑒𝑙 = 𝜈̅ = √
2𝜋𝑐 𝜇
√1−(𝑉⁄𝐶 )2

𝑐
𝐸 = ℎ𝜈 𝑣=
𝜆

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20
IR Spectroscopy Table

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