NATIONAL INSTITUTE OF TECHNOLOGY, ROURKELA-8

END SEMESTER EXAMINATION, 2021

SESSION: 2020 - 21, SPRING SEMESTER
PROGRAMME: Integ M.Sc & M.Sc Chemistry SEMESTER: 8th & 2nd Eighth & second)
Dept. Code: CY Course Code: CY-4202
Course Name: Advanced Topic in Inorganic Chemistry

Duration of Examination: 02.00 hours

Answer all questions

Figures in the right hand margin indicate marks
All parts of a question should be answered at one place
Q. No Marks
1a. Match the complex ions in Column I with the appropriate lowest energy d-d transition listed 1
in Column II.
Column I Column II
P. [V(H2O)6] 2+
1. A2g → 3T2g
2

Q. [Ti(H2O)6]3+ 2. 4A2g → 4T2g

R. [Ni(H2O)6]2+ 3. 2T2g → 2Eg

(i) P-2, Q-1, R-3, (ii) P-3, Q-1, R-2 (iii) P-1, Q-3, R-2 (iv) P-2, Q-3, R-1

b. Considering the -bonding only, in the MO diagram of metal complex with trigonal 1
pipyramidal (TBP) geometry, the d orbitals which remain non-bonding are
i) dz2, dxz ii) dxz, dyz iii) dx2-y2, dxy iv) dz2, dyz

c. The electronic spectrum of [V(H2O)6]3+ complex has two absorption bands (indicates correct 3
assignment of bands), one at 17,800 cm-1 (1) and the second at 25,700 cm-1 (2), using the
Tanabe–Sugano diagrams estimate the values of o and B for this complex.
2a. [Ni(dma)6]2+ (dma = dimethylacetamide) complex showed three electronic transitions 2
frequencies (in cm-1), 1 (7576), 2 (12,739), and 3 (23,809). Determine the values 0 and the
Racah parameter B.
b. The Mulliken symbols for the spectroscopic states arising from the free-ion term F are 1
(i) T2g + Eg (ii) T1g + T2g + T1u (iii) T1g + T2g + A2g (iv) A1g + T2g + T1g

c. i) [CoCl4]2- and CdS shows a deep blue colour because of 1+1

….……….……and…………….…….transitions, respectively
ii) what do you expect the energy of metal to ligand charge-transfer bands to increase or
decrease with increasing charge on the complex for the following isoelectronic series
[V(CO)6]¯, Cr(CO)6, and [Mn(CO)6]+ complexes. Explain
3a. Monothiocarbamate Fe(III) complexes (structure given below) of have been prepared. For 2

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 the methyl and ethyl complexes, the magnetic moment, , is 5.7 to 5.8 B at 300 K; it
changes to 4.70 to 5 B at 150 K, and drops still further to 3.6 to 4 B at 78 K. The color
changes from red to orange as the temperature is lowered. With larger R groups (propyl,
piperidyl, pyrrolidyl),  > 5.3 B at all temperatures and greater than 6 B in some. Explain
these changes.

b. In the solid state, Co(py)2Cl2 is violet and has a magnetic moment of 5.5 BM, but a CH2Cl2 2
solution of this compound is blue and has a magnetic moment of 4.42 BM. In contrast,
Co(py)2Br2 is blue in both the solid state and in a CH2Cl2 solution and has a magnetic
moment of 4.6 BM in both forms. Explain these observations. Predict the colors and
magnetic moments of Co(2-Mepy)2Cl2 and Co(py)2I2. (py = Pyridine)
c. 1
Why trivalent lanthanide ions mostly show narrow band emission?
4a. What is nephelauxetic effect and give a proof for the exsiting covalent bonding of metal 3
complexes by using the same.
b. Find the ground state term symbol for Sm3+, Dy3+, Er3+ and Eu3+ ion 2

5a. Give the reason why Eu2+ shows broad emission, whereas Eu3+ shows narrow band emission. 1

b. The linker Naphthalene monoimide dithiolates was used between the photosensitizer and the 2
active site for proton reduction. Give the reason why the linker is important.

c. The octahedral high spin complex [Cr(H2O)6]2+ shows one UV/Vis absorption band. Assign 2
the transition by using an Orgel diagram.
6a. 2
Synthesis cis-platin from [PtCl4]2¯ by utilizing the trans-effect.

b. 1
The reactions of [PtCl4]2¯ with NH3 (reaction I) and of [PtCl4]2¯ with [NO2]¯ followed by
NH3 (reaction II) are ways of preparing:

i) I: trans-[PtCl2(NH3)2]; II: trans-[PtCl2(NH3)(NO2)]¯ ii) I: cis-[PtCl2(NH3)2]; II: trans-

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 [PtCl2(NH3)(NO2)]– iii) I: cis-[PtCl2(NH3)2]; II: cis-[PtCl2(NH3)(NO2)]¯ iv) I: trans-
[PtCl2(NH3)2]; II: cis-[PtCl2(NH3)(NO2)]–

c. 1
In the base-catalyzed substitution of Cl¯ by [OH]– in [Co(NH3)5Cl]2+ under strongly basic
conditions, the first step in the mechanism is:
i) conversion of an ammine to amido ligand ii) substitution of Cl– by [OH]– iii) dissociation
of Cl– to give a 5-coordinate intermediate iv) association of [OH]– to give a 7-coordinate
intermediate

d. The 1st step in the Eigen-Wilkins mechanism for ML6 undergoing Y for L substitution is: 1

i) loss of L ii) addition of Y iii) formation of a weakly bound encounter complex

iv) formation of a 7-coordinate complex in the rate-determining step

7a. Explain the mechanism of pseudocontact and true contact shift. In addition, which NMR 3
shift reagent (complexes) give high and down-field shift in NMR spectrum.

b Which of the following ligands could not act as a bridging ligand for the inner-sphere 1
electron transfer reaction?
i) 1,10-phenanthroline ii) 4,4'-bipyridine iii) pyrazine iv) bis(4-pyridyl)methane

c. Would you expect the rate to increase or decrease if you replaced the ancillary (spectator) 1
water ligands by CH3OCH3 (dimethyl ether)? Explain your answer.
8a. The correct order of rate of exchange of water molecule between coordination sphere and 0.5
Bulk is i) Cr3+ < Al3+ < Cr2+ < Ni2+ ii) Cr3+ < Al3+ < Ni2+ < Cr2+ iii) Cr3+ < Ni2+ < Cr2+ <
Al3+ iv) Cr3+ < Cr2+ < Al3+ < Ni2+

b. Lability of the ions should follow the order 0.5

i) Cr2+ > Mn2+ > V2+ ii) Mn2+ > Cr2+ > V2+ iii) Mn2+ > V2+ > Cr2+ iv) V2+ > Cr2+ >
Mn2+

c. Consider the statements A-D regarding equations I-III 1

I) [Fe(CN)6]3¯ + [Co(CN)5] 3¯  [Fe(CN)6]6¯ + [Co(CN)5]2¯

II) [Co(bipy)3]2+ + [Co*(bipy)3]3+  [Co(bipy)3]3+ + [Co*(bipy)3]2+

III) [Co(NH3)5F]2+ + [Cr(H2O)6]3+  [Co(NH3)5F]3+ + [Cr(H2O)6]2+

(A) Marcus equation is applicable to I and II, (B) Marcus equation is only applicable to II,
(C) Equations I and II involve inner sphere electron transfer, (D) Equations I and III involve

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 inner sphere electron transfer, the correct statements are:

i) A and B ii) B and C iii) B and D iv) C and D

d. What is the difference between the Trans-effect and Trans-influence? 3

9a. Which of the following statements are true for the lanthanides? 0.5
A. The observed magnetic moment of Eu3+ at room temperature is higher than that calculated
from spin-orbit coupling B. Lanthanide oxides are predominantly acidic in nature C. The
stability of Sm(II) is due to its half-filled sub-shell D. Lanthanide (III) ions can be separated
by ion exchange chromatography
(i) A and D (ii) A and B (iii) A and C (iv) B and C

b. Which one of the following pairs consists of a good oxidizing and a good reducing agent 0.5
respectively: i. Ce(IV), Ln(III) ii) Ln(III), Eu(II) iii) Ce(IV), Eu(II) iv) Ln(III), Ce(III)

c. What is the ground term for d4 (low spin)? 0.5

d. Lanthanoid hydrides of formula LnH2: 0.5

i) contain the lanthanoid metal in oxidation state +2 ii) are electrically conducting materials
iii) possess 3-dimensional covalent structures iv) are mixed valence Ln(I)/Ln(III)
compounds
e. Draw the energy level diagram and explain the energy transfer process for the Eu(tta)3.H2O 2
complex.

f. Match the lanthanide ions given in column A with fluoroescence colours given in column B 1
Column A Column B
i) Dy(III) a) Blue
ii) Eu(III) b) Green
iii) Tb (III) c) Red
iv) Tm(III) d) Yellow

10a. The recoil energy of a Mössbauer nuclide of mass 139 amu is 2.5 MeV. The energy emitted 1
by the nucleus in keV is (i) 12.5 (ii) 15.0 (iii) 20.5 (iv) 25.0

b. For a tetragonally distorted Cr(III) complex, zero-field splitting results in the following 1
number of Kramers doublets (i) 1 (ii) 2 (iii) 3 (iv) 4

c. Draw the EPR spectrum of vanadyl acetylacetonate 2

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d. To record Mössbauer spectrum of Fe containing sample a source X is used. X after the 0.5
nuclear transformation gives  radiation used in MB spectroscopy

i) 57Fe, -emission ii) 57Co, -emission iii) 57Co, e capture iv) 57Fe, e capture

e. Which of the following species is ESR-active? 0.5

i) VOSO4 ii) K2Cr2O7 iii) KMnO4 iv) [Co(NH3)6]Cl3

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