RAMAKRISHNA MISSION VIDYAMANDIRA

(Residential Autonomous College affiliated to University of Calcutta)

M.A./M.Sc. FIRST SEMESTER EXAMINATION, DECEMBER 2019
FIRST YEAR [BATCH 2019-21]
Date : 12/12/2019 APPLIED CHEMISTRY
Time : 11 am – 1 pm Paper : I (Inorganic Chemistry) Full Marks : 50

(Use a separate Answer Book for each Unit)

UNIT-I

Answer any five questions: [5  5]

1. a) State the factors on which the energy gap between t2g and eg levels of an octahedral complex
depend. [3]
b) Pick up the ions which will under go John-Teller distortion. Give reasons for your choice.
Fe3  HS  , Co2  LS  , Ni 2 , and Cr 2  HS  [2]
2. What is Orgel diagram? Give the Orgel diagram for a d2 ion showing probable transition. [1+4]
3. a) Write down the expression for the CFSE of the following complexes:
Fe  CN 6 , Au  CN 4 and CoCl42
3 
[3]
b) OH ion is in lower postion than in H2O in spectrochemcial series – Explain. [2]
4. a) Why K3 CuF6  is paramagnetic while K  AgF4  is diamagnetics? [3]
3
 FeF6  is colourless white  Fe  CN 6  is coloured – Explain.
3
b) [2]
3
5. a) In electronic spectrum of Ti  H 2O 6  shows a broad band having peak at 20,100 cm-1 and
shoulder at 17400 cm-1. Assign the ligand field transition for both the peak and the shoulder for
H2O as ligand. [3]
3
b) For the complex  Mn  H 2O 6  , the mean pairing energy (p) is found to be 28,800 cm-1. The
magnitude of 10Dq  or  is 21000 cm-1. Calculate the CFSE for the complex corresponding to
high spin and low spin state. [2]
6. a) Comment on the following magnetic moments : (a) K3 CoF6  has   4.2BM but K3 CuF6  has
2.8 B.M and K 2  NiF6  is diamagnetic. [3]
b) What is meant by the symbol 3F? Show that it represents a total degeneracy (orbital plus spin) of
21. [2]
7. a) Using MO theory, explain how is  -value influenced by (i) ligands; acting as  -donor and (ii)
ligands acting as  -acceptor. [3]
b) Explain the term 'nephelauxtic effect'. Iodide ion is more nephelauxitic than CN- - Why? [2]
2
8. The greenish blue aqueous solution of  Ni  H 2O 6  show the absorption peaks at
wavenumbers 8700 cm-1,14500 cm-1 and 25300 cm-1. Assign the bonds in Orgel diagram and
hence estimate the value of 10 Dq of the complex. [3+2]
9. a) Though the d-d transition is Lapste-forlidden yet some colour of weak intensity is found in
Centro symmetric molecules –why? [2]

(1)
 b) Depict the d-orbital splitting patterns in the complexes VO  acac 2 and Ni  CN 4 .
2
[3]
10. a) Explain the terms 'outer orbital' and 'inner orbital' complexes with example. [3]
b) Explain why is Fe  O  Phen 3 species deep red.
2
[2]

UNIT-II
Answer any one question: [1  13]

10. a) Give a brief account of the structural differences between cytochromes 'a','b' and 'c' and explain
the slow rate of electron transfer in cytochrome C. [3+3]
b) State the biological function of Fe-S proteins. [3]
c) Give brief introduction on Wilson disease and Parkinson's disease. [2+2]

11. a) Elucidate the role of Cis-platin in therpeutic use with necessary justification and explain the
adverse effect of it. [3+1]
b) Explain the role of magnesium (II) and Mn (II) protein in photosynthesis. [2+2]
c) In which form arsenic is more toxic and why. [2]
d) What is Rubredoxine? Explain the colour of its oxidised and reduced form. [1+2]

UNIT-III
Answer any one question: [1  12]

12. Consider the 18e rule as a guide and determine

a) The M-m bonds in the following complexes.
i) Co2  CO 4 (ii)  CO 2 Rh    cl 2 Rh  CO 2 [2]
b) Re2 gCl82 cluster is highly coloured : Explain. [2]
c) Discuss the structure and bonding of Zeise's Salt. [3]
d) The IR stretching frequencies v  CO  cm  in CO, Mo  CO 6 , Mo  CO 3  NH 3 3 and
1

Mo  CO 3  PPh3 3 are 2143,2004,1950 cm-1 respectively. Give reason for the absorption. [3]
e) How can you prepare aldehyde by Wacker process? Give mechanism. [3]

13. a) Discuss the necessary condition for Metal cluster formation. [3]
b) Classify following metalloboranes /metalcarbonylate by structural type.
2
i) B4 H 6  CoCP 2 ii)  Re4  CO 16  [2]

c) How many M-M bonds are present in  Mo2 

4
[2]
d) How is ferrocine prepared? Mention its structure. How would you convert ferrocene into
diacetye acetate compound? [3]
or
The C NMR spectrum in the CO region at 65o c of the cluster Cp3 Rh3  CO 3 giving a triplet
13

but at temp +26oc a13

2 quarte result. Discuss the structure of the cluster .

e) What is Zeigler-Natta catalyst. Give one uses. [2]

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