University of Bahr el Ghazal

College of Education
Department of Chemistry

Course: EDC 313 Inorganic Chemistry (III)

Academic year 2021-2022 Main Examinations 3rd Year/First Semester (2024)

Instructions: Read the instructions carefully

1. Time: 2hrs
2. Answer all the questions in sections A, B and two questions in section C.
3. Answered each question in its separate page as recommended at the first
cover page of the answer-sheet.

Section A: answer all the questions (20 marks)

Q.1) Choose the correct answer in each of the following questions (10 marks)
I. Which one of the following statements does not fit the definitions of the d-
block/transition elements?
(A) Elements situated between s- and p-block elements in the long form of
periodic table.
(B) Elements that exhibit intermediate chemical properties between s and p
block elements.
(C) Elements that have an incomplete d subshell in either the neutral atomic or
ionic state.
(D) The elements whose atoms receive the last electron in the d2 sp3 orbitals.

II. One the following statement best explain the diminish seen in atomic size
from scandium to nickel across the period, which one?
(A) Increased attraction between the outer electrons and increasing nuclear
charge along the period.
(B) Maximum number of unpaired d-d electrons available for bonding.
(C) Increased attraction between the core electrons and decreased atomic
charge down the group
(D) Maximum number of paired d-d electrons available for bonding.
III. The intervention of the 4f orbital, that is, the filling of 4f orbital before 5d
orbital results in a regular decrease in atomic radii. This phenomenon is
called ………………
(A) Halogenic effect. (B) Lanthanoid contraction
(C) Amphoteric effect. (D) Screening rule
IV. What is the number of the secondary valence in ൣCr(H2 O)6 ൧Cl3 ?
(A) 5 (B) 6 (C) 1 (D) 3
V. Magnetic moment is determined by the number of unpaired electrons and is
calculated by using the ‘spin-only’ formula, i.e., …………………………….
(A) ඥn(n + 2) BM. (B) Hψ = E ψ
(𝐂) CFSE = ቀnet2g ቁ ൫−0.4∆O ൯ + ቀneeg ቁ ൫0.6∆O ൯ (𝑫) ටn(n + 3)
Q.2) Define the following terms (10 marks).
(I) Coordination Chemistry
Branch of inorganic chemistry that deals with the study of coordinated
compounds or complexes.
Branch of inorganic chemistry that deals with the study of compounds that do
not dissociate into their constituent ions in any solvents.
(II) Chelate ligand
Ligands that bind via more than one atom and form complexes.
(III) Transition elements
A transition element is defined as the one which has incompletely filled d
orbitals in its ground state or in any one of its oxidation states. i.e., A transition
element should have partially filled (n-1) d orbital.
(IV) Hydrate isomerism
Exchange between water molecule inside the coordination sphere and ions present
in the ionization sphere is called hydrate isomerism.
(V) Inner coordination sphere
The central metal atom and the ligands directly attached enclosed in a square
bracket are collectively termed as inner coordination sphere.

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 Section B: answer all the questions (30 marks)

Q. 3 A) Why do most d-block elements form stable complexes. (3 marks)

Transition metals form a large number of complex compounds due to
1. comparatively smaller sizes of the metal ions,
2. their high ionic charges, and
3. the availability of d orbitals for bond formation.

B) Comparatively, nuclear volume of transition elements is much lower than those

of s- and p-block elements. Explain. (3 marks)

As (n-1) d orbitals are being filled, atomic charge expands pulling the electrons
internally, and hence nuclear volume diminishes. That means the nuclear volume
of transition elements is much lower than those of s and p block elements.

With decline in the nuclear volume, nuclear thickness of these elements increases
and therefore, d-b lock elements show higher densities compared to s- and p-block
elements…not necessary

C) 𝑃𝑒𝑛𝑡𝑎𝑎𝑚𝑖𝑛𝑒𝑛𝑖𝑡𝑟𝑜𝑐𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼) and 𝑃𝑒𝑛𝑡𝑎𝑎𝑚𝑖𝑛𝑒𝑛𝑖𝑡𝑟𝑖𝑡𝑜𝑐𝑜𝑏𝑎𝑙𝑡(𝐼𝐼𝐼) are

linkage isomers. Illustrate this structural isomerism. (3 marks)

(a) Pentaaminenitrocobalt(III). (b) Pentaaminenitritocobalt(III)

Nitro isomer (N is the donor atom). Nitrito isomer (O is the donor atom)

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Q 4) Use [𝐹𝑒(𝐶𝑁)6 ]3− complex to answer all the questions below (8 marks).
a) Determine the oxidation state
Oxidation state of M can be calculated as
𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑀 + 𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝐿 × 𝑛 = ± 𝑜𝑟 0
Therefore; 𝐹𝑒 + (−1 × 6) = −3 ∴ 𝐹𝑒 = −3 + 6 = +3
b) What is the coordination number of the metal ion of this complex?
CN is number of ligands around the central metal atom. In the above complex,
CN is 6.
c) Determine the type of hybridization of this complex
Solution:

The resulting complex is inner orbital, octahedral.

d) Is this complex ion a cation or an anion?

By negative charge of the complex, it is an anionic complex
e) Use the IUPAC system to name this complex: Hexacyanoferrate(III)
complex
f) Is this complex paramagnetic or diamagnetic?
Due to presence of one unpaired electron, it is paramagnetic.
g) What is the effective atomic number of the central atom?
EAN equals metal/ionic atomic number plus number of electrons donated by
ligands or 2 times number of ligands (as each ligand can donate 2 electrons).
Therefore, Fe (Z=26); 𝐹𝑒 +2 (Z=24). There are 6 L*2=12
Hence, EAN=24+12=36 (Atomic number of krypton)

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 h) Calculate CFSE for [𝐹𝑒(𝐶𝑁)6 ]3−
Iron in its ground state is [𝐴𝑟]3𝑑6 4𝑠 2 , in its charge state (𝐹𝑒 +2 ) state it will be a
𝑑 6 system with 𝑡2𝑔6 𝑒𝑔0 . Configuration of electrons because 𝐶𝑁 − CN- is a strong
field ligand. Therefore, CFSE be
−0.4 ∆𝑂 𝑋 6 + 2𝑃 = − 2.4 ∆𝑂 + 2𝑃
Q 5 A) The magnetic moment of a certain 𝐶𝑜(𝐼𝐼) complex is 4.0 𝜇𝐵. What is its d-
electron configuration? (3 marks)
Solution
A 𝐶𝑜(𝐼𝐼) complex is 𝑑 7
Two possible configurations: 𝑡2𝑔5 𝑒𝑔2 . (high-spin, S=1½) with 3
unpaired electrons or 𝑡2𝑔6 𝑒𝑔1 . (Low-spin, S=½) with1unpaired
electron.
The spin-only magnetic moments are 3.87 𝜇𝐵 and 1.73 𝜇𝐵.
Therefore, the only consistent assignment is the high-spin
configuration 𝑡2𝑔5 𝑒𝑔2 .
B) Illustrate which one is diamagnetic: [𝑁𝑖(𝐶𝑁)4 ]2− or [𝑁𝑖(𝐶𝑙)4 ]2− (10 marks)
Being four coordinate complexes:

The resulting complex is tetrahedral with two unpaired electrons, and therefore,
paramagnetic.

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The resulting complex is square planar and diamagnetic.

Section C Essay questions: answer only two (2) (20 marks)

Q 6) Draw M.O diagram for [𝑇𝑖(𝐻2 𝑂)6 ]3+ octahedral complex. Explain the
formation of bonding, nonbonding and antibonding MOs and comment on its
magnetic properties. (10 marks).
Hexaaqua titanium (III) ion [𝑇𝑖(𝐻2 𝑂)6 ]3+
In this complex, central metal ion is 𝑇𝑖 3+ and surrounding neutral ligand is 𝐻2 𝑂.
1) M.O. Diagram:

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2) Explanation:
During the formation of this complex, 3d, 4s & 4p orbitals of 𝑇𝑖 3+ ions are
available for linear combination with LGOs. Thus, 𝑎1𝑔 , 𝑡1𝑢 & 𝑒𝑔 orbitals of 𝑇𝑖 3+
ions combine with 𝑎1𝑔 , 𝑡1𝑢 & 𝑒𝑔 LGOs to form six bonding molecular orbitals
𝑎1𝑔 , 𝑡1𝑢 & 𝑒𝑔 and six antibonding molecular orbitals 𝑎1𝑔∗ 𝑡1𝑢∗ , t1u* & 𝑒𝑔∗ . While
𝑡2𝑔 remain non-bonding 𝑡2𝑔𝑛 ,

3) Electronic Configuration (EC) of metal ion:

𝐸. 𝐶. 𝑜𝑓 𝑇𝑖 (𝑍 = 22): 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑 2 4𝑠 2 1s2, 2s2, 2p6, 3s2, 3p6, 3d 2,
4s2 Or [𝐴𝑟] 3𝑑 2 4𝑠 2
E.C. of 𝑇𝑖 3+ (𝑍 = 19): 1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑1 4𝑠 0 Or [𝐴𝑟] 3𝑑1 4𝑠 0
4) Filling of electrons:
a) In all 13 electrons are involved in complex formation; one from Ti+3 ion and
12 from six ligands.
b) These electrons are then filled in MOs according to Aufbau principle. The
electrons are first filled in lower energy bonding molecular orbitals and then
higher energy orbitals are occupied.
c) Thus, the E.C. of this complex is: 𝑎1𝑔2 , 𝑡1𝑢6 , 𝑒𝑔4 , 𝑡2𝑔1
5) Magnetic Character: In this complex, one unpaired electron is present in MO.
Therefore, this complex is paramagnetic in nature.

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 3−
Q 7) Discuss in detail the formation of ൣCoF6 ൧ ion as a six-coordination
complex according to the valency bond theory, VBT (10 marks).
Solution
3−
In ൣCoF6 ൧ ion,
Co atom E.C: [𝐴𝑟]4𝑠 2 3𝑑7
Co (III) ion: E.C: [𝐴𝑟]4𝑠 0 3𝑑 6
Determining the hybridization of this complex

Co G.S:
3d 4s 4P

Co3+
3d 4s 4P

3−
ൣCoF6 ൧

3d 4s 4P

F− F− F− F− F− F−
𝑑 2 𝑠𝑝3
The resulting complex is inner orbital, octahedral and due to the absence of
unpaired electron, it is diamagnetic.

Q 8) Using crystal field theory, draw the crystal field diagram for 𝐹𝑒 3+ 𝑖𝑜𝑛 in
high-spin and low spin complexes. Use your diagram to answer the following
questions (10 marks)
Solution
CFT Diagram for 𝐹𝑒 3+ 𝑖𝑜𝑛 in high-spin and low spin.

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(A) Calculate the CFSE in both high-spin and low-spin.
CFSE is the energy difference for the given electron configuration in the
crystal field compared to the spherical (isotropic) field:

(B) Calculate the magnetic moment in both high-spin and low spin.
√𝑛 + (𝑛 + 2): 𝐼𝑛 ℎ𝑖𝑔ℎ − 𝑠𝑝𝑖𝑛: √5(5 + 2) = 5.92𝐵𝑀
𝐼𝑛 𝑙𝑜𝑤 𝑠𝑝𝑖𝑛: √0(0 + 2) = 1.4𝐵𝑀
(C) Give one example of ligand that favors high-spin and one ligand that favors low-spin.
Strong-field ligand such as cyanide favors low spin while weak-field ligand such as
Chloride favors high-spin

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WISH YOU SUCCESS!

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