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Learning Outcomes-based Curriculum Framework (LOCF) for

Post-graduate Programme

M.Sc. Programme in Chemistry

(Specialisation in Renewable Energy)

(Syllabus effective from 2020 Admission onwards)

UNIVERSITY OF KERALA
Department of Chemistry
2020
1
PREAMBLE
The role of higher education is vital in securing the gainful employment and providing further access to
higher education comparable to the best available in the world-class institutions elsewhere. The
improvement in the quality of higher education, therefore, deserves to be given tom-most priority to enable
the young generation of students to acquire skill, training and knowledge to enhance their thinking,
comprehension and application abilities and prepare them to compete, succeed and excel globally.
Sustained initiatives are required to reform the present higher education system for improving and
upgrading the academic resources and learning environments by raising the quality of teaching and
standards of achievements in learning outcomes across all undergraduate programs in science, humanities,
commerce and professional streams of higher education.
One of the significant reforms in the undergraduate education is to introduce the Learning Outcomes-
based Curriculum Framework (LOCF) which makes it student-centric, interactive and outcome-oriented
with well-defined aims, objectives and goals to achieve. The University Grants Commission (UGC) took the
initiative of implementing the LOCF in the Colleges and the Universities of the country. Accordingly, the
University of Kerala has decided to implement the LOCF in all its departments under the auspices of
Internal Quality Assurance Cell (IQAC). A series of teacher training workshops were organised by IQAC
and the office of the Credit and Semester System (CSS), and the departments have revised the syllabus
accordingly, through workshops and in consultation with academic experts in the field.

GRADUATE ATTRIBUTES (GAs)


The Graduate Attributes (GAs) reflect particular qualities and abilities of an individual learner including
knowledge, application of knowledge, professional and life skills, attitudes and human values that are
required to be acquired by the graduates of University of Kerala. The graduate attributes include capabilities
to strengthen one’s professional abilities for widening current knowledge and industry-ready skills,
undertaking future studies for global and local application, performing creatively and professionally, in a
chosen career and ultimately playing a constructive role as a socially responsible global citizen. The
Graduate Attributes define the characteristics of learners and describe a set of competencies that are beyond
the study of a particular area and programme.
The GAs of University of Kerala
 Continue life-long learning as an autonomous learner
 Continuously strive for excellence in education
 Apply and nurture critical and creative thinking
 Promote sustainable development practices
 Promote co-operation over competition
 Balance rights with responsibilities
 Understand and respect diversity & difference
 Not be prejudiced by gender, age, caste, religion, or nationality.

2
 Use education as a tool for emancipation and empowerment of humanity

BRIEF HISTORY OF THE DEPARTMENT

The origin of the Department of Chemistry may be traced to the establishment of the University of
Travancore, 1937. It currently offers M.Sc., M.Phil. and Ph.D. programmes and is one of the active
teaching and research departments in the state. The M.Sc. programme was named as M.Sc. Analytical
Chemistry when it started in the year 1960, and later converted to M.Sc. in Chemistry in 1997. The
faculty members, past and present, and the alumni have made valuable contribution to the teaching and
research in chemistry. Theirprestigious recognitions include the Vice Chairmanship of UGC, Directorship
of NAAC, Vice-Chancellorships at M. G. and IGNO Universities, Humboldt Foundation Fellowships, DAAD
Fellowship, Fogarty NIH Travel Award and Bhatnagar Award.

3
UNIVERSITY OF KERALA
DEPARTMENT OF CHEMISTRY
Syllabus for M.Sc. Chemistry

Programme Specific Outcomes (PSO) for M.Sc. Chemistry

PSO 1 Develop asolid understanding on the fundamental principles and major concepts
in the core disciplines of chemistry with the ability to analyze at an advanced
level
PSO 2 Generate an understanding on the importance of application of Chemisry in
academic, industrial, environmental and social context.
PSO 3 Provide an intellectual training to develop a rational and rigorous scientific
approach in synthesizing information and concepts.
PSO 4 Develop skills to handle modern analytical and spectroscopic instruments.
PSO 5 Equip the students to perform standard laboratory procedures, monitor by
observation and measurement events or changes and record data.
PSO 6 Develop research and analytical skills in basic research with the ability to
undertake research in multidisciplinary teams.
PSO 7 Provide a detailed training in written and verbal communication of scientific
information and ideas
PSO 8 Develop ability to work independently or as part of a team in a research setting
to adapt to wide range of available career option in the future.

PSO=Program Specific Outcome


R=Remember
Un=Understanding
Ap=Apply
An=Analyse
E=Evaluate
C=Create
FK=Factual Knowledge
CK=Conceptual Knowledge
PK=Procedural Knowledge
MK=Metacognitive Knowledge

4
Programme Structure of M.Sc. Chemistry

Course Name of the course Core Discipline- Generic Skill


Semester

Code Course Specific Course Enhancement

Credits
s (CC) Elective (GC) Elective (SEE)
(DSE)
Core Courses (CC)
CHE-CC-511 Inorganic Chemistry I + 3
CHE-CC-512 Organic Chemistry I + 3
CHE-CC-513 Physical Chemistry I + 3
I CHE-CC-514 Inorganic Chemistry Lab + 3
I
CHE-CC-515 Organic Chemistry Lab I + 3
CHE-CC-516 Physical Chemistry Lab + 3
I
CHE-CC-521 Inorganic Chemistry II + 3
CHE-CC-522 Organic Chemistry II + 3
CHE-CC-523 Physical Chemistry II + 3
CHE-CC-524 Inorganic Chemistry Lab + 3
II
CHE-CC-525 Organic Chemistry Lab + 3
II II
CHE-CC-526 Physical Chemistry Lab + 3
II
Discipline-Specific Elective (DE)
CHE-DE-527 Advanced Inorganic + 2
Chemistry
CHE-DE-528 Advanced Organic + 2
Chemistry
CHE-DE-529 Advanced Physical + 2
Chemistry
Core Courses (CC)
CHE-CC-531 Inorganic Chemistry III + 3
CHE-CC-532 Organic Chemistry III + 3
CHE-CC-533 Physical Chemistry III + 3
CHE-CC-534 Inorganic Chemistry Lab + 3
III
III CHE-CC-535 Organic Chemistry Lab + 3
III
CHE-CC-536 Physical Chemistry Lab + 3
III
Discipline-Specific Elective (DE)
CHE-DE-537 Electronic Structure + 3
Theoryand Applications

5
CHE-DE-538 Photophysical + 3
Processesand
Applications
CHE-DE-539 New Methods in + 3
Organic Synthesis
CHE-DE-540 Introduction to Chemical + 3
Biology and Anti-
Cancer Research
IV Core Courses (CC)
CHE-CC-541 Comprehensive Viva + 2
CHE-CC-542 Dissertation + 14
Discipline-Specific Elective (DE)
CHE-DE-543 Applied Chemistry + 3
CHE-DE-544 Analytical and + 3
Instrumental Methods
Generic Course (GC)
Any Sem

CHE-GC-501 Analytical and + 2


Environmental
Chemistry

6
FIRST SEMESTER

1. Semester 1
2. Course Title INORGANIC CHEMISTRY I
3. Course Code CHE-CC-511
4. Credits 3
5. CO: On completion of the course, students should be able TL KL PSO No.
to:
1. Describe the fundamentals of coordination chemistry and its 1-R, 2-Un, FK PSO1
significance 3-Ap
2. Describe the importance of inorganic chemistry in biological 2-Un, 3-Ap FK, PSO1, PSO2
systems and process CK
3. Explain the concept of acid strength and reactions in non- 2-Un, 3-AP FK, PSO1, PSO3
aqueous condition 4-An CK
4. Memorize and explain the chemistry of noble gases and 1-R, 2-Un FK, PSO1, PSO3
halogens 3-Ap CK
MOD. COURSE CONTENT CO No.
No
I Introduction to Coordination Chemistry: Types of ligands and complexes. CO1
Coordination number and geometry: Classification of complexes based on
coordination numbers and possible geometries. Isomerism: Structural,
geometrical and optical isomerism. Stability of complex ions in aqueous
solution: Formation constants. Stepwise and overall formation constants.
Factors affecting stability of complexes. Determination of stability constants.
Irving William order of stability, Chelate and macrocyclic effects.
II Theories of Structure and Bonding in Metal Complexes: Valence bond theory CO1
and its limitations. Ligand field theory: Splitting of d orbitals in different ligand
fields such as octahedral, tetragonal, square planar, tetrahedral,
trigonalbipyramidal and square pyramidal fields. Jahn Teller effect. LFSE and
its calculation. Thermodynamic effects of LFSE. Factors affecting the splitting
parameter. Spectrochemical series. Molecular orbital theory based on group
theoretical approach and bonding in metal complexes. MO diagrams of
complexes with and without π bonds. Effect of π bond on the stability of the
complex. Sigma and pi bonding ligands such as CO, NO, CN-, R3P, and Ar3P.
Nephelauxetic series.
III Bioinorganic Chemistry: Essential and trace elements in biological systems, CO2
structure and functions of biological membranes, mechanism of ion transport
across membranes, sodium pump, ionophores, valinomycin and crown ether
complexes of Na+ and K+. Photosynthesis-chlorophyll a, PS I and PS II. Z-
scheme of photosynthesis. Role of manganese complex in oxygen evolution.
Coordination compounds in medicine- Anticancer drugs: Platinum complexes-
cisplatin. Various types of interaction of metal complexes with nucleic acids.
IV Oxygen carriers and oxygen transport proteins-Hemoglobins, myoglobins and CO2
hemocyanin, hemerythrins and hemevanadins, Iron-Sulphur proteins. Nature
of heme-dioxygen binding. cooperativity in hemoglobin. Iron storage and
transport in biological systems-ferritin and transferrin. Redox metalloenzymes-
cytochromes, peroxidases and superoxide dismutase and catalases.
NonredoxmetalloenzymesCarboxypeptidaseA and Carbonic anhydrase –
structure, function and mechanism of action. Nitrogen Fixation nitrogenase,

7
vitamin B12 and the vitamin B12 coenzymes.
V Acid-Base Chemistry and Chemistry in Non-aqueous Solvents: Relative CO3
strength of acids, Pauling rules, Lux-Flood concept, Lewis concept,
Measurement of acid base strength systematics of Lewis acid-base
interactions steric and solvation effects acid – base anomalies , Pearson’s
HSAB concept, acid- base strength and hardness and softness, Symbiosis,
theoretical basis of hardness and softness, electronegativity and hardness.
Chemistry in non-aqueous solvents, reactions in NH3, liquid SO2, solvent
character, reactions in SO2, acetic acid, solvent character, reactions in
CH3COOH and some other solvents. Molten salts as non-aqueous solvents,
solvent properties, room temperature molten salts, unreactivity of molten
salts, solutions of metals.
VI Chemistry of noble gases and halogens: Early chemistry, Xenon fluorides and CO4
oxofluorides; Synthesis, properties, structure and bonding. Xenon compounds
with bonds to other elements. Chemistry of Krypton and Radon. Chemistry of
halogens: Halogens in positive oxidation states. Interhalogen compounds,
pseudohalogens and polyhalide ions including polyiodide anions.
References:
rd
1. Banerjea, D. “Coordination Chemistry”, 3 Edn., Asian books, 2009.
th
2. Cotton, F. A. and Wilkinson, G., “Advanced Inorganic Chemistry”, 6 Edn, Wiley Interscience, New York, 1999.
th
3. Huheey, J. E. Keiter, E. A. and Keiter, R. L. “Inorganic Chemistry - Principles of Structure and Reactivity”, 4 Edn,
HarperCollins, New York., 1993.
4. Kettle, S. F. A. "Physical Inorganic Chemistry: A Coordination Chemistry approach", Oxford University press,
2000.
5. Lippard, S. J. and Berg, J. M. “Principles of Bioinorganic Chemistry”, University Science Books, 1994.
th
6. Atkins, P. W. and Shriver, D. F. “Inorganic Chemistry”, 5 Edn, OUP, 2009.
7. Bertini, I, Gray, H. B., Lippard, S. J. and Valentine, J. S., “Bioinorganic Chemistry”, University science books, 1994.
nd
8. Cowan, J. A. “Inorganic Biochemistry - An Introduction”, 2 Edn.,Wiley-VCH, 1997.
9. Figgis, B. N and Hitchman, M. A. “Ligand Field Theory and its Applications,” Wiley-India, 2010.

Additional References
10. Holleman, A. F. and Wiberg, E. “Inorganic Chemistry”, Academic press, 2001.
11. Lee, J. D. “Concise Inorganic Chemistry,” 4th Edn., Wiley-India, 2008.
12. Purcell, K.F and Kotz, J. C. “Inorganic Chemistry”, Holt-Saunders, 2010.
rd
13. Reddy, B. E. Douglas, D. H. McDanial and .Alexander, J. J “Concepts and Models of Inorganic Chemistry”, 3 Edn,
John Wiley, 2001.
14. Reddy, K. H. “Bioinorganic Chemistry”, New Age international, 2003

8
Model Question Paper

FIRST SEMESTER M.Sc. DEGREE EXAMINATION Month Year


Branch: CHEMISTRY
CHE-CC-511: INORGANIC CHEMISTRY I

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. What is meant by step-wise formation constant of a complex? In the formation of the


complex [ML4] show that β4 = K1.K2.K3.K4.
2. Give a note on Irving William order of stability.
3. Which ligand makes higher ∆0 value; H2O or OH– ? Justify your answer.
4. Which one exhibits higher nephelauxetic effect; NH3 or CN– ? Substantiate your answer.
5. Give a short note on ionophores.
6. Trans-platin has no anticancer activity, though Cis-platin is a promising anticancer drug.
Why ?
7. Distinguish between ferrintin and transferrin.
8. Discuss the role of P cluster in Nitrogenase.
9. Indicate the conjugate acids of the following : i) NH3 ii) NH2– iii) H2O iv) HI
10. ‘Liquid ammonia is called a levelling solvent.’ Justify the statement.
11. Why are the O-F bonds in O2F2 longer than OF2 whereas the O-O bond in O2F2 is short
compared with that in H2O2 ?
12. Draw the structure of XeF2, XeF4 and XeF6.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Draw the structure of Cis and trans – dichloro-bis(ethylene diamine)Cobalt(III) ion.
Which isomer is optically active ? Justify your answer.
14. Chelate effect is an entropy effect. Justify the statement.
15. Discuss about the various factors affecting the magnitude of splitting parameter (∆) in
complexes.
16. What is valinomycin ? How can you explain that valinomycin binds K+ more tightly than
Na+ ?
17. Discuss the structural features and function of Catalase.
18. Give a brief note on Iron-Sulphur proteins.
19. With suitable examples, explain the utility of molten salts as solvent in reactions.

9
20. Give the structure of IF5. How does IF5 reacts with XeF2 and XeF4 ? Liquid IF5 conduct
electricity. What is the reason behind it ?

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Discuss the merits of MOT over CFT and sketch the MO diagram for [CoF6]3– and
predict its magnetic behavior.
22. i) Describe the classification of complexes based on co-ordination numbers and
geometry.
ii) Compare the structure and function of any two zinc containing enzymes in mammals.
(4 + 4)

23. Illustrate the z-scheme of photosynthesis.

24. i) Discuss the effect of substituents on the strength of Lewis acids and bases.

ii) Give an account of polyhalide ions. (4 + 4)

10
1. Semester 1
2. Course Title ORGANIC CHEMISTRY I
3. Course Code CHE-CC-512
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Recognize and predict the nature and reactivity of organic molecules 1-R, 2-Un FK, CK I, III
2. Assess the stability of various conformers of acyclic and cyclic systems 3-Ap, 4-An FK, CK I, II
3. Identify and differentiate prochirality and chirality at centers, axis, 3-Ap, 4-An FK, CK I, III
planes and helices and designate the stereocenters and prochiral centers
4. Appreciate and apply the stereochemical implications on addition, 2-Un, 3-Ap FK, CK II, III
substitution and elimination reactions
5. Comprehend the reactivity of carbonyl groups towards base mediated 2-Un, 3-Ap FK, CK II, III
condensation reactions
6. Write the mechanisms of organic reactions involving reactive 5-E, 6-C CK III
intermediates
MODULE COURSE CONTENT CO No.
No
I Structural Organic Chemistry - Aromaticity, Hückel’s rule, criteria for 1
aromaticity, annulenes, mesoionic compounds, metallocenes, cyclic carbocations
and carbanions, anti- and homo- aromatic systems, Fullerenes, Carbon
nanotubes and graphenes, Physical organic chemistry - kinetic and
thermodynamic control of reactions, Hammond’s postulate, kinetic isotope
effects with examples, linear free energy relationships, Hammett and Taft
equations, Curtin-Hammett principle, Catalysis by acids and bases with
examples like acetal, cyanohydrin, ester formations and hydrolysis reactions,
Acidity and Basicity of organic compounds, pKa values, kinetic and
thermodynamic acidity. Hard and soft acids and bases - HSAB principle and its
applications.
II Stereochemistry of Organic Molecules - Conformational analysis of alkanes and 2, 3
cycloalkanes, Effect of conformation on reactivity of cyclohexane and decalin
derivatives. Anomeric effect, Sawhorse and Newmann projections, Geometrical
isomers, E-Z nomenclature, Molecular symmetry and chirality, chiral centres –
enantiomers and diastereomers, CIP rules. R and S, threo, erythro
nomenclatures, non-carbon chiral centres, Axial and Planar chirality,
Atropisomerism, Helicity, stereochemical descriptors for chiral axis and planes,
Prostereoisomerism, topicity, Stereoselective and stereospecific reactions,
regioselective and regiospecific reactions, calculation of enantiomeric excess
and specific rotation, Chiral separation methods, Chiral shift reagents, non-
carbon chirality.
III Reactions of sp3 Carbons - Stereochemical and mechanistic aspects of SN 3
reactions, Effect of solvent, leaving group and substrate structure, Neighbouring
group participation, Non-classical carbocations and ion pairs in SN reactions,
Ambident nucleophiles and substrates, SN′ and SNi reactions, Isotopic and salt
effects, Formation and ring opening of epoxides in cyclohexyl systems (Fürst
Plattner rule). Elimination reactions leading to C=C bond formation. E1, E2 and
E1CB mechanisms, Hoffman and Saytzeff modes of elimination, Effect of
leaving group and substrate structure, Pyrolytic eliminations – Chugaev and
Cope eliminations, Cis eliminations. Substitution vs elimination.

11
IV Reactions of sp2 Carbon and Aromatic Systems - Electrophilic addition to C=C - 4
Mechanistic and stereochemical aspects of bromine addition, halolactonization,
hydrogenations, hydroborations, epoxidation including Sharpless asymmetric
epoxidation, hydroxylations including Woodward-Prevost hydroxylations, oxy-
mercuration and de-mercuration and singlet carbene addition. Stereochemistry of
addition to C=O systems. Cram, Cram-chelate, Felkin-Anh and Houk models.
Zimmerman-Traxler transition states, Desymmetrization and kinetic resolution,
Methods of determining absolute configuration, Aromatic electrophilic and
nucleophilic substitutions, Electronic and steric effects of substituents. SN1,
SNAr, Benzyne and SRN1 mechanism and their evidences.
V Reactions of carbonyl compounds - Aldol and mixed-aldol condensations, 5
Claisen, Reformatsky, Perkin, Stobbe, Darzens, Knoevenagel, Dieckmann,
Thorpe, Henry and Mannich reactions, reductions of carbonyl group
(Clemmenson and Wolff-Kishner), Addition of cyanide, ammonia, alcohol and
Grignard reagents, Structure, synthesis and reactions of α,β – unsaturated
carbonyl compounds, Michael addition and Robinson annulation, Prins reaction.
VI Rearrangement Reactions - Structure, stability and formation of carbocations 6
and carbanions, Classical and non-classical carbocations, Rearrangements
including Wagner-Meerwein, Pinacol-Pinacolone, Dienone-Phenol, Beckmann
and Benzidine, Baeyer-Villiger oxidation, Demjanov ring expansions, Favorskii
and Benzilic acid rearrangements, Ramburg-Buckland reaction, Peterson and
Julia olefinations, Structure and synthesis of phosphorus, sulphur and nitrogen
ylides, Reactions of ylides including Wittig reaction. Structure, stability and
formation of carbenes, nitrenes and benzynes. Bamford-Stevens reaction,
Simmon-Smith reaction, Shapiro reaction, Wolff rearrangement, Arndt-Eistert
homologation, Hofmann, Curtius, Lossen and Schmidt rearrangements. Addition
and insertion reactions of carbenes and nitrenes, Nucleophilic aromatic
substitutions and cycloadditions of benzynes.

REFERENCES
 Peter Sykes “A guidebook to mechanism in organic chemistry”, Longman, 6thEdn.
 Smith, M. B. and March, J. "March’s Advanced Organic Chemistry", 6thEdn, Wiley. 2007.
 Kalsi, P. S. "Stereochemistry and Reaction Mechanisms", Wiley Eastern, 2005
 Nasipuri, D. "Stereochemistry of Organic Compounds – Principles and Applications", 3rd Edn, New
Age International, 2018
 ROC Norman and JM Coxon, “Principles of Organic Synthesis”, CRC Press, 3rd En, 1993.

ADDITIONAL REFERENCES
 Clayden, J., Greeves, N and Warren, S. “Organic Chemistry”, OUP, 2001
 Carey, F. A. and Sundberg, R J. “Advanced Organic Chemistry - Part A: Structure and
Mechanisms”,5th Edn, Springer, 2007.
 K. Peter, C. Vollhardt and NE Schore, “Organic Chemistry – Structure and Function”, Freeman, 2003
 Lowry, T.H. and Richardson, K. S. “Mechanism and Theory in Organic Chemistry” 3rd Edn, Harper
Row, 1987.
 PS Kalsi “Stereochemistry and Mechanism Through Solved Problems” New Age International, 2001
 Moody, C. J. and Whitham, W. H. "Reactive Intermediates", 1992, OUP.
 McMurry, “Organic Chemistry”, Thomson Brooks/Cole, 1999.

12
Model Question Paper

FIRST SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-CC-512 : ORGANIC CHEMISTRY I

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

21. Arrange the following in the increasing order of aromaticity and justify: furan, pyridine,
thiophene and pyrrole.
22. Depict the structure of the product formed when S-2-butanol is treated with thionyl chloride.
Explain the mechanism of the reaction by providing suitable illustration.
23. “Hydroboration oxidation follows anti-Markownikov addition”. Justify the statement providing
suitable example.
24. Arrange the following in the increasing order of nucleophilicity and justify your answer: 4-nitro
phenol, phenol, 3-chloro phenol and 4-methyl phenol
25. Predict the product/products with correct stereochemistry formed when bromine adds to cis-2-
butene.
26. Compare the E1 and E1cB mechanisms providing suitable examples.
27. Depict the conformation of cis-4-t-butyl-1-methyl cyclohexane and cis-decalin
28. What is atropisomerism?. Illustrate with an example.
29. Suggest and illustrate a method to convert bromo benzene to biphenyl.
30. Suggest methods to convert cyclobutanone to γ-lactam and γ-lactone.
31. Predict the products when cyclohex-2,3-enone reacts separately with sulphonium ylide and
sulphoxonium ylide.
32. Apply Cram’s rule to identify the major product formed by the reaction of methyl magnexium
bromide with (S)-2-phenyl propionaldehyde.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

33. Provide R/S notation for the following molecules.


EtO2C

(a)
(CH2)n
CO2Et

(d)
O
(c)

(b)

34. 2(R)-Hydroxy, 3(S) bromo butane when treated with a small amount of base yields compound A.
Identify the structure of compound A and show the correct stereochemistry, reaction scheme and
mechanism.
35. In each pair of similar substitution reactions below write the structures of the products of each;
indicating which reaction is likely to have the faster rate and why.

13
i) Phenylmethyl chloride (benzyl chloride) or 2-phenylethyl chloride with silver acetate in
methanol ii) Sodium cyanide in acetone with 1-methyl-1-idomethyl-cyclopentane or 2-
cycopentylethyl iodide iii) 2-phenyl-2-propanol or 3-phenyl-2,4-dimethyl-3-pentanol on warming
in concentrated HBr iv) Sodium salt of methyl malonate and ethyl iodide in methanol or in
acetonitrile (CH3CN)
36. Explain briefly Curtius, Hoffmann, Lossen and Schmidt rearrangements.
37. Predict the products from the following reactions
NNHTs
Ph

(i) HNO2 base (iii) heat


NH2 (ii) O N3
OH

Ph SeO2
(iv)
H2O

38. The following reactions take place in acid medium: Illustrate the mechanisms involved.

O O
(ii)
(i) 4
O
OH
39. Predict the products when cyclohex-2,3-enone reacts separately with sulphonium ylide,
sulphoxonium ylide, SeO2 and CH2I2-Zn.
40. Explain the aromaticity in annulenes with examples.

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21 i) Distinguish between stereoselective and stereospecific reactions with suitable examples


ii) How can hyperconjugation explain the stability of substituted alkenes? (4 +4)
22. i) In the following reactions, decide whether it is likely to proceed by S N1 or SN2 mechanisms.
Predict the products including the stereochemistry
a) S-1-Pheny1-1-bromobutane + NaCN in dimethylformamide
b) S-1-Pheny1-1-bromobutane + AgOAc in ethanol
ii) Give 2 mechanisms for nucleophilic aromatic substitutions providing suitable examples.
(4+4)

23. Identify A – D providing the mechanism for each reaction.

P(OEt)3 SO2Ph KNH2


A B
liq NH3
NO2 Cl
O O
Cl
NaOH peracid
C D
MeOh H+

24. Depict the schemes with reagents and illustrate the mechanisms of Perkin, Stobbe, Dieckmann and
Knoevenagel reactions.

14
1. Semester 1
2. Course Title PHYSICAL CHEMISTRY I
3. Course Code CHE-CC-513
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Describe and justify the importance of Quantum Mechanics 1-R; 5-E FK,CK I
2. Understand and apply various postulates in deriving property 2-Un;3- CK,PK I, II
operators and Schrodinger equation Ap
3. Derive the Schrodinger equation of particle in a box, HO, RR and H- 1-R; 2- FK,CK I, II, III
atom and interpret the results Un
4. Identify the symmetry elements and operators and determine the 1-R; 5-E CK,PK I, II, III
correct point group
5. Construct the character table and apply this to characterize the 3-Ap; 6- CK,PK I, II, III
molecular vibrations and hybrid orbitals. Cr
6. Understand various adsorption isotherms and its use in surface 2-Un; 3- FK,CK I, II
area measurements Ap
7. Understand the concept of colloidal material and their stability for 2-Un FK I, II
many practical use
8. Explain various techniques to study the surfaces 2-Un CK I, II
MODULE COURSE CONTENT CO No.
No
I Historic evolution of quantum mechanics: The wave nature of sub-atomic particles. The 1,2
uncertainty principle and its consequences. The postulates of quantum mechanics. Wave
functions, well-behavedness, Orthogonality theorem. Orthonormality. Concept of
operators: Laplacian, Hamiltonian, linear and Hermitian operators. Angular momentum
operators and their properties. Operator algebra, Commutators, Eigen function and eigen
values. Expectation value. Time dependent and independent Schrodinger equation.
Separation of variables.
II Exactly solvable problems: Solutions of Schrodinger wave equations for: 3
1. A free particle in 1D. Particle in 1D box of infinite and finite potential wells.
Tunnelling. Particle in 3D box. Zero point energy and significance. Applications in
conjugated dyes.
2. 1D- Harmonic oscillator. Hermite equation and Hermite polynomials. Recurrence
formula. 3D- harmonic oscillator. Oscillator model and Molecular vibrations.
Selection rule for vibrational transitions.
III Schrodinger equation in polar coordinates and exactly solvable problems: Solutions of 3
Schrodinger wave equations for
1. Rigid rotator. Particle on a ring. Separation of variables. Real and Imaginary Wave
functions.
2. Non-planar rigid rotator. Legendre and Associated Legende equations and
polynomials. Rodrigue’s formula. Spherical Harmonics. Polar Diagrams. Salient
features. Space quantization.
Hydrogen atom. Laguerre and Associated Laguerre equations and corresponding
polynomials. Space quantization. Zeeman effect, Uhlenbeck and Goudsmith postulate of
spin, Stern Gerlach experiment. Orbitals and Spin orbitals. Radial probability distribution
function and graphs. Selection rules for spectral transitions.
IV Symmetry and character tables: Symmetry elements and symmetry operations. Point 4,5

15
groups. Multiplication of operations. Conditions for a set of elements to form a group.
Group multiplication table. Similarity transformation and classification of symmetry
operations. Matrix representation of point group. Reducible and irreducible
representations. Character of a matrix. Orthogonality theorem. Rules derived from
orthogonality theorem (proof not required). Setting up of the character tables of simple
groups - C2V, C2h, C3V and C4V on the basis of the rules. Reduction of reducible
representations to irreducible representations. Molecular dissymmetry and optical
activity. Applications of character tables to spectroscopy. Transition moment operators,
vanishing integrals, determination of number of active IR and Raman lines. Application of
character table to orbitals. Construction of hybrid orbitals. Construction of Symmetry
adapted LCAO
V Types of surfaces. Measurements of surface pressure and surface potential. Surfactants 6
and micelles. The gas-solid interface. Types of adsorption. Heat of adsorption. Adsorption
isotherms. Gibbs adsorption equation and its verification. Langmuir isotherm. Multilayer
adsorption. Freundlich isotherm. BET isotherm. Solid-liquid interface. Influence of surface
tension on adsorption. Measurements of surface area of solids.Harkin-Jure method.
Entropy and point B methods. Use of Langmuir isotherm and BET method. Eley-Rideal
mechanism and the Langmuir-Hinshelwood mechanism
VI Colloids- zeta potential, electrokinetic phenomena, sedimentation potential and streaming 7,8
potential, Donnan membrane equilibrium. Emulsions: macro- and micro-emulsions; aging
and stabilization of emulsions; Phase behaviour of microemulsions. Surface Enhanced
Raman Scattering, Surfaces for SERS studies, Chemical enhancement mechanism, Surface
selection rules, Applications of SERS. Application of low energy electron diffraction and
photoelectron spectroscopy, ESCA and Auger electron spectroscopy, scanning probe
microscopy, ion scattering, SEM and TEM in the study of surfaces.
References:


th
Levine, I. N., "Quantum Chemistry", 7 Edition, Pearson Education Inc., 2014.

nd
McQuarrie, D. A., "Quantum Chemistry", 2 Edition,University Science Books, 2008.
 Szabo, A.; Ostlund, N. S. “Modern Quantum Chemistry: Introduction to Advanced Electronic Structure theory”,
Dover Publications, 1996.

rd
Cotton, F. A., "Chemical Applications of Group Theory", 3 Edition, Wiley-Interscience, 1990.
 AlexanderA. andJohnsonP., “Colloid Science,” Oxford University Press, New York, 1996.
 Raj, G. Surface Chemistry (Adsorption), 4th Edition, Goel Publishing House, 2002.

nd
GreggS. J., “The Surface Chemistry of Solids”, 2 Edition, Chapman Hall, 1961.
 Jaffe, H.H.; Orchin, M., "Symmetry in Chemistry", Dover Publications, 2002.

ADDITIONAL REFERENCES
nd
 Pillar, F. L. “Elementary Quantum Chemistry”, 2 Edition, Dover Publication, 2001.
 Chandra, A. K., "Introduction to Quantum Mechanics", 4 Ed, Tata McGraw-Hill, New Delhi, 2003.
th

 Prasad, R. K., “Quantum Chemistry”, 4 Edition, New Age International, 2009.


th

 Gopinathan M. S.; Ramakrishnan, V., "Group Theory in Chemistry" 2 Edition, Vishal Publications, 2013.
nd

 Somorjai, A., “Introduction to Surface Chemistry and Catalysis”, 2 Edition, Wiley-Interscience, 2010.
nd

16
Model Question Paper

FIRST SEMESTER M.Sc. DEGREE EXAMINATION, Month Year


Branch: CHEMISTRY
CHE-C513: PHYSICAL CHEMISTRY-I
Times: 3 Hours Max. Marks: 60

SECTION- A

Answer any 10 questions. Each question carries 2 marks.

1. Prove that the Hermitian operator always has real eigen values.
2. Normalize the function sin(kx) and eikx in the interval x = 0 and x = 2π.
3. Calculate the quantum number of a particle of mass of 1g in a 10cm length box having energy kT at
room temperature.
4. Explain the term ‘degeneracy’. Give a schematic sketch of the first three energy levels
obtained in particle in 3D-cubic box indicating their degeneracy.

5. Prove that the nonexistence of zero point energy in planar rigid rotator is not in violation of
Heisenberg’s uncertainty principle.
6. Set up the Schrodinger equation for hydrogen atom in spherical polar coordinates.
7. What different point groups may the biphenyl molecule belong to depending on the rotational
relationship of the two rings about the C-C bonds?
8. Explain with an example a) Symmetry Operation (b) Symmetry element.
9. Discuss the effect of temperature on chemisorption.
10. Find out the number of collisions that would occur on a catalyst surface when it
is exposed to Helium gas at 100 micropascals and 2000C.
11. What are the factors determining emulsion stability?
12. Enumerate two applications of Auger Electron Spectroscopy.

SECTION- B
Answer any 6 questions. Each question carries 4 marks.
13. Explain the postulates of quantum mechanics.
14. Calculate the expectation value of the x-position of a particle in the state n=2 of a one-dimensional
box of length L.
15. a) Write down the radial equation R(r) for H atom. Derive the general solution for R(r) when r is
very large (r--> ∞) and very small (r-->0)?
16. For the D3h point group, classify each of the representation into Raman, IR active and both Raman
and IR active.
D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1 x2+y2,z2

A2’ 1 1 -1 1 1 -1 Rz

E’ 2 -1 0 2 -1 0 (x,y) (x2-y2,xy)

17
A1” 1 1 1 -1 -1 -1

A2” 1 1 -1 -1 -1 1 z

E” 2 -1 0 -2 1 0 (Rx,Ry) (xz,yz)

17. State the great orthogonality theorem. Explain how it is essential in constructing the character
table?
18. A monolayer of N2 is adsorbed on 1g of a catalyst powder at liquid nitrogentemperature. Upon
warming N2 occupied a volume of 3.86 cm3 at 00C and 1 atmpressure. What is the surface area
of the catalyst ? The effective area of N2 molecule is 0.167 nm2 ( Given N = 6.023 E + 23)
19. Calculate adsorption enthalpy when a fixed volume of gas is adsorbed on a particular catalyst for
following data (R=8.31 JK-1 mol-1)

P/torr 30 40
T(K) 200 240

20. How can you determine the type of emulsions? Explain one of the methods.
SECTION C

Answer any two questions. Each question carries 8 marks


21. a) Set up and solve the Schrodinger equation of motion for a SHO. Deduce the expressions for
energy.
b) Find the hybridization of O in H2O using the C2v character table.

C2v E C2z σv(xy) σv(yz)

A1 1 1 1 1 z x2,y2,z2

A2 1 1 -1 -1 Rz xy

B1 1 -1 1 -1 x,Ry xz

B2 1 -1 -1 1 y,Rx yz (4+4)

22. a) Write down the Schrodinger equation for H-atom in spherical polar coordinates and separate the
variables.
b) What is the probability of finding the electron within radius of a0 from the nucleus (Given ground
state wave function of H-atom is (1/πa03)1/2e-r/ a0) (4+4)

23. a) Discuss Gibbs adsorption eqauation.


b) Deduce the BET adsorption isotherm. (4+4)
2
24. a) Calculate the expectation values of Px and Px for a particle in 1-dimensional box.
Rationalize the results.
b) The 1s orbital of H-atom is given by the expression 1s= (1/πa03)1/2e-r/ a0), where a0 is the
Bohr radius. Show that the most probable radius at which the electron will be found in the 1s
orbital is a0. (4+4)
18
1. Semester 1
2. Course Title Inorganic Chemistry Lab I
3. Course Code CHE-CC-514
4. Credits 3
5. CO: On completion of the course, students should be able TL KL PSO No.
to:
1. Achieve hand on experience in inorganic experiments 3-Ap CK, PK, PSO5, PSO6
particularly separation of metal ions and identification from 4-An MK
their binary mixture
2. Demonstrate various volumetric analysis independently 4-An CK, PK, PSO5, PSO6
5-E MK
3. Describe the principles behind various volumetric analysis 2-Un FK, CK PSO1, PSO3
MOD. COURSE CONTENT CO No.
No.
I Separation and identification of rare/less familiar metal ions such as Ti, W, Se, CO1
Mo, Ce, Th, Zr, V, U and Li in their binary mixtures.
( A student must analyse at least 6 samples)
II Quantitative volumetric estimations of various metal ions using EDTA. CO2, CO3
III Volumetric quantitative estimations using ammonium vanadate. CO2, CO3
IV Volumetric quantitative estimations using cerium (IV) sulphate (Cerimetry). CO2, CO3
V Quantitative volumetric estimations using chloramine-T. CO2, CO3
VI Volumetric quatitative estimations using potassium iodate CO2, CO3
(A student must do a total of at least 8 volumetric estimations).
References:
1. Skoog, D. A. and West, D. M. "Analytical Chemistry: An Introduction", Saunders.
3. Vogel, A. I. "A Text Book of Qualitative Inorganic Analysis", Longman.
4. Vogel, A. I. “A Text Book of Quantitative Inorganic Analysis", Longman.

19
1. Semester 1
2. Course Title ORGANIC CHEMISTRY LAB I
3. Course Code CHE-CC-515
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Separate products formed in organic reactions using solvent 2-Un, FK, PK I, V
extraction (if possible) 4-An
2. Work-up organic reactions using suitable solvents 3-Ap PK I, V
3. To do synthesis of solid derivatives of the compounds separated 1- R, FK, PK III, V
3-Ap
4. Carry out distillation, sublimation and re-crystallization 3-Ap PK I, V
5. Find out the Rf values of compounds by TLC analysis 4-An FK, CK, V, VI
PK
6. Purify compounds by simple column chromatography 3-Ap FK, PK I, V
MODULE COURSE CONTENT CO No.
No
I Quantitative wet chemistry separation of a mixture of two components 1, 2
by solvent extraction using ether. Separation of acidic component from
basic component. Identification of the separated compounds
II Separation of acidic/basic component from neutral component. 1, 2
Identification of the separated compounds by functional group
analysis,
III Preparation of derivatives for acidic, basic and neutral components like 3
esters, anhydrides, amides, picrates, hydrazonesetc
IV Separation by distillation method. Ordinary distillation and vacuum 4
distillation, Separation by sublimation and crystallization methods.
V Separation of binary mixtures of organic compounds using TLC. 5
Identification using RF values, Identification of number of products in
a reaction mixture, different methods for TLC visualization
VI Separation of binary mixtures by column chromatography. Packing a 6
column, loading of sample and elution. TLC visualization and removal
of the solvent to collect the pure fraction, Demonstration of HPLC
technique.

REFERENCES
 S. P Bhutani, ArunaChhikara “Practical Organic Chemistry - Qualitative Analysis” ANE Books,
New Delhi
 Ahluwalia, V. K. and Aggarwal, R. “Comprehensive Practical Organic Chemistry” Vol 1 & 2,
Universities Press.
 Bell, C. E. Taber, D. F. and Clark, A. K. “Organic Chemistry Laboratory”, Thomson.
 Pasto, D. J. Johnson, C. R. and Miller, M. J. “Experiments and Techniques in Organic
Chemistry”, Prentice Hall.

20
1. Semester 1
2. Course Title PHYSICAL CHEMISTRY LAB I
3. Course Code CHE-CC-516
4. Credits 3
5. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Understand the concept of solubility and apply it to calculate 2-Un; 3-Ap CK,PK IV; V
distribution coefficients and concentration of unknown.
2. Use refractometer to measure the refractive index 3-Ap CK,PK V; VI
3. Measure the kinetic rate of hydrolysis of esters 5-Ev CK,PK V;VI
4. Use calorimeter to determine heats of reactions 3-Ap;5-Ev CK,PK V; VI
5. Use efficiently the polarimeter 3-Ap CK,PK V;VI
6. Understand the basic principles of lab techniques adopted in 2-Un FK V, VII, VIII
physical Laboratories,monitor, record and present data in a
scientific form
MODULE COURSE CONTENT CO No.
No
I Distribution law: Partition of iodine, ammonia and aniline between water and organic 1,6
solvents. Association of benzoic acid. Equilibrium constants of Tri-iodide and copper-
ammonium complexes. Enthalpy change for tri-iodide formation.
II Refractometry: Refractive index and molar refraction of liquids. Atomic refractions. 2,6
Composition of solid solutes. Molecular and ionic radii from molar refraction. Study of the
complex K2[HgI4].
III Chemical kinetics: Acid hydrolysis of esters. Comparison of strengths of acids. 3,6
Saponification of esters. Persulphate-iodide second order reaction. Activation energy.
Arrhenius parameters. Primary salt effect.
IV Thermochemistry: Determination of water equivalent. Heat of neutralization and heat of 4,6
ionization. Integral and differential heats of solution. Thermometric titrations.
Determination of concentrations of strong acids.
V Polarimetry: Inversion of cane sugar. Velocity constants for different acid strengths. 5,6
Comparison of strengths of two acids.
VI Adsorption: Verification of Langmuir and Freundlich isotherms for solute adsorption on 6
solids. Estimation of surface area. First order kinetics. Computation of adsorption
thermodynamics. Exothermic and endothermic reactions.
References:
 Daniels,F. and Mathews,J. H. "Experimental Physical Chemistry", McGraw Hill, 1970.
 Finlay, A. and Kitchener,J. A. "Practical Physical Chemistry", Longman, 1977.
 James,A. M. "Practical Physical Chemistry", Longman, 1981.
 Shoemaker, D. P. and Garland,C. W. "Experiments in Physical Chemistry", McGraw Hill, 1998.

th
Willard,H. H. Merritt , L. L. and Dean,J. A. "Instrumental Methods of Analysis" 7 Edition, CBS Publishers, 2004..
 Viswanathan, B.; Raghavan, P. S. “Practical Physical Chemistry,” Viva Books, 2004.

21
SECOND SEMESTER

1. Semester 2
2. Course Title INORGANIC CHEMISTRY II
3. Course Code CHE-CC-521
4. Credits 3
5. CO: On completion of the course, students should be able TL KL PSO No.
to:
1. Describe and compare the electronic, spectral and magnetic 2-Un, 4- FK, PSO1, PSO3
properties of metal complexes An, 5-E CK
2. Execute their fundamental knowledge in co-ordination 3-Ap, 4- FK, PSO1, PSO3
chemistry to understand and evaluate properties of various An, CK
metal complexes 5-E
3. Classify and distinguish the stability and reactivity of metal 4-An, 5-E FK, PSO1, PSO2
complexes CK
4. Explain and demonstrate the coordination chemistry of 4-An, 5-E FK PSO1, PSO2
lanthanides and actinides CK
5. Describe, demonstrate and compare the fundamental concepts 2-Un, 4- FK PSO1, PSO2
of organometallic chemistry An, 5-E CK
6. Explain and examine the reactions of various organometallic 3-Ap, 4-An FK, PSO1, PSO2
complexes 5-E CK PSO3
7. Evaluate the applications of organometallic complexes in 4-An, 5-E FK, PSO2,PSO3
various domains CK
MOD COURSE CONTENT CO No.
No
I Electronic Spectra of complexes-Term symbols of dn system. Racah CO1, CO2
parameters, splitting of terms in weak and strong octahedral and tetrahedral
fields. Correlation diagrams for dn and d10-n ions in octahedral and tetrahedral
fields (qualitative approach), d-d transition, selection rules for electronic
transition-effect of spin orbit coupling and vibronic coupling. Orgel diagrams.
Tanabe Sugano diagrams. Effects of Jahn Teller distortion and spin orbit
coupling on spectra. Charge transfer spectra. luminescence spectra.
II Magnetic properties of metal complexes: Types of magnetism shown by CO1, CO2
complexes- paramagnetic and diamagnetic complexes, molar susceptibility,
Magnetic susceptibility measurements. Gouy method. Spin only value. Orbital
contribution to magnetic moment. Temperature dependence of magnetism-
Curie’s law, Curie-Weiss law. Temperature Independent Paramagnetism (TIP),
Ferromagnetism and antiferromagnetism in complexes. Anomalous magnetic
moments. Elucidating the structure of metal complexes (cobalt and nickel
complexes) using electronic spectra, IR spectra and magnetic moments.
III Reactions of Metal Complexes: Kinetics and mechanism of reactions involving CO3
complexes in solution. Inert and labile complexes. Kinetics and mechanism of
nucleophilic substitution (Ligand displacement) reactions in square planar
complexes. trans effect-theory and applications. Kinetics and mechanism of
octahedral substitution, Dissociative and associative mechanisms, Ligand field
effects on reaction rate. Influence of acid and base on reaction rate.
Racemization and isomerization. Redox reactions in complexes: Electron
transfer and electron exchange reactions. Theories of Electron transfer
reactions-outer sphere mechanism-Marcus theory, inner sphere mechanism,
electron transfer in metalloproteins.

22
IV Coordination Chemistry of Lanthanides and Actinides: General characteristics CO4
of lanthanides-Electronic configuration, Term symbols for lanthanide ions,
Oxidation state, Lanthanide contraction. Factors that mitigate against the
formation of lanthanide complexes. Electronic spectra and magnetic properties
of lanthanide complexes. Lanthanide complexes as shift reagents. General
characteristics of actinides-difference between 4f and 5f orbitals, comparative
account of coordination chemistry of lanthanides and actinides with special
reference to electronic spectra and magnetic properties.
V Organometallic Compounds-Synthesis, Structure and Bonding: Compounds CO5
with transition metal to carbon bonds, classification of ligands, eighteen
electron rule. Organometallic compounds with linear pi donor ligands-olefins,
acetylenes, dienes and allyl complexes-synthesis, structure and bonding.
Complexes with cyclic pi donors-metallocenes and cyclic arene complexes
structure and bonding. Carbene and carbyne complexes. Preparation,
properties, structure and bonding of simple mono and binuclear metal
carbonyls, metal nitrosyls, metal cyanides and dinitrogen complexes.
Polynuclear metal carbonyls with and without bridging.
VI Reactions of Organometallic Compounds: Substitution reactions-nucleophilic CO6, CO7
ligand substitution, nucleophilic and electrophilic attack on coordinated
ligands. Addition and elimination reactions-1,2 additions to double bonds,
carbonylation and decarbonylation, oxidative addition and reductive
elimination, insertion (migration) and elimination reactions. Catalysis by
organometallic compounds: Homogeneous and heterogeneous organometallic
catalysis-alkene hydrogenation using Wilkinson catalyst. Reactions of carbon
monoxide and hydrogen-the water gas shift reaction, the Fischer-Tropsch
reaction (synthesis of gasoline). Hydroformylation of olefins using cobalt or
rhodium catalyst. Carbonylation reactions-Monsanto acetic acid process,
carbonylation of butadiene using Co 2(CO)8 catalyst in adipic ester synthesis.
Palladium catalysed oxidation of ethylene-the Wacker process.
References:
1. Banerjea, D. “Coordination Chemistry”, 3rd Edn., Asian books, 2009.
2. Cotton, F. A. and Wilkinson, G. “Advanced Inorganic Chemistry”, 6th Edn, Wiley
3. Cotton, S. “Lanthanide and Actinide Chemistry”, John Wiley & Sons, 2007.
4. Dutta, R. L and Syamal, A. “Elements of Magnetochemistry”, 2nd Edn., East West press, 1993.
5. Huheey, J. E. Keiter, E. A. and Keiter, R. L. “Inorganic Chemistry - Principles of Structure and Reactivity”, 4th Edn,
HarperCollins, New York., 1993.
6. Kettle, S. F. A. "Physical Inorganic Chemistry: A Coordination Chemistry approach", Oxford University press, 2000.
7. Mehrotra, R. C. and Singh, A. “Organometallic Chemistry: A Unified Approach”, New age international, 2007.
8. Purcell, K. F. Kotz, J. C. ‘Inorganic Chemistry”, Holt-Saunders, 2010.
9. Sathyanarayana, D. N. “Electronic Absorption Spectroscopy and Related Techniques”, Universities press, 2001.
th
10. Miessler, G. L., Fischer, P. J and Tarr, D. A “ Inorganic Chemistry” 5 edn. Pearson, 2014.

Additional references
11. Bailar, J. C. "Chemistry of Coordination Compounds", Reinhold, 1956.
12. Basolo, F. Pearson, R. G. “Mechanisms of Inorganic Reaction”, John Wiley & Sons, 2006.
13. Crabtree, R. H. “The Organometallic Chemistry of Transition Metals”, 2Edn, Wiley.
14. Guptha, B. D. Elias, A. J “Basic Organometallic Chemistry”, Universities Press, 2010.
15. Holleman, A. F. and Wiberg, E. “Inorganic Chemistry”, Academic.
16. Lever, A. B. P. “Inorganic Electronic Spectroscopy”, 2nd Edn., Elsevier, 1984.
17. Lewi, E. s and Wilkins, R. G. (Eds.), "Modern Coordination Chemistry", Interscience, 1967.
18. Wilkins, R. G. “Kinetics &Mechanism of Reactions of Transition Metal Complexes”, 2Ed, VCH.

23
Model Question Paper

SECOND SEMESTER M.Sc. DEGREE EXAMINATION Month Year


Branch: CHEMISTRY
CHE-CC-521: INORGANIC CHEMISTRY II

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. [Ti Cl6]3- and [Ti (CN)6]3- gives λmax at 13,000 cm-1 and 22,300 cm-1 in their respective
electronic spectra. Justify the statement.
2. The term symbols for d3 and d4 configuration is 4F. Explain.
3. Predict the geometries and magnetic moments of [Ni Cl4]2- and [Ni (CN)4]2- on the basis
of valence bond theory.
4. Calculate the magnetic moment for [Co Cl4]2- taking into account the fact that there is
angular momentum contribution to the magnetic moment. (Δ = 3100 cm-1).
5. Which isomer of [Pt (NH3)2 Cl2] is formed when [Pt (NH3)4]2+ is reacted with 2 moles of
HCl? Why?
6. ‘The inert complexes are not necessarily thermodynamically stable’. Justify this
statement with an example.
7. Lanthanides ions give rise to very sharp bands in their electronic spectra. Why?
8. Yttrium is concentrated along with lanthanides; why?
9. Draw the structures of the following 18 electron compounds and mention the hapticity of
organic ligands:
i) [Mn (CO)4 (C3H5)] ii) [Fe (CO)2 Cp (CH3)]
10. The IR stretching frequency of CO in metal carbonyls is lower than that for free CO
molecule. Why?
11. What are oxidative addition and reductive elimination reactions, as applied to
organometallic chemistry?
12. Write a catalytic cycle for the synthesis of acetic acid from methanol.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Discuss the spectral consequence of Jahn- Teller distortion in transition metal complexes.
14. The electronic spectrum of [Co (NH3)6]3+ has a weak band in the red – and two medium
intensity bands in the visible to near UV region. Assign these transitions using Orgel
diagram.

24
15. What is spin-only magnetic moment? How it is useful in the structural elucidation of
transition metal complexes?
16. Illustrate the mechanism of inner-sphere electron transfer reactions using a specific
example.
17. What is trans effect? What is its theoretical basis?
18. Discuss the bonding in metal nitrosyls.
19. ) Exemplify and briefly discuss the structure and bonding in cyclic arene complexes.
20. Draw and discuss the catalytic cycle for hydroformylation of alkenes using rhodium
complex as catalyst.

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Write briefly on Tanabe-Sugano diagrams with special reference to their construction and
advantages in the interpretation of electronic spectra.
22. i) Discuss briefly about the temperature dependence on magnetism.
ii) What is meant by aquation reaction? Using suitable examples, explain the mechanism
of aquation reactions of octahedral complexes.
(4 + 4)
23. Compare lanthanide and actinide complexes based on their oxidation state, electronic
spectra and magnetic properties.

24. i) Discuss the general methods of preparation of metal carbonyls.

ii) Illustrate the mechanism of oxidation of ethylene using Wacker process.

(4 + 4)

25
1. Semester 2
2. Course Title ORGANIC CHEMISTRY II
3. Course Code CHE-CC-522
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Comprehend the reactivity pattern of free-radicals 2-Un, FK, CK I
4-An
2. Understand the orbital interactions and apply orbital symmetry 2-Un, FK, CK I, III
correlations of various pericyclic reactions 3-Ap
3. Understand photochemistry of molecules 2-Un, FK I, II,
3-Ap III
4. Write the mechanisms of organic reactions involving free-radicals 3-Ap, CK, MK III
and concerted reactions 5-E
5. Apply NMR, IR, MS, UV-Vis spectroscopic techniques to solve 3-Ap CK, MK III,
structure of organic molecules and in determination of their VI
stereochemistry.
6. Interpret the spectroscopic data of unknown compounds. 3-Ap, CK, MK VI
5-E
MODULE COURSE CONTENT CO No.
No
I Radicals in Organic Synthesis - Structure, stability and generation of 1, 4
free radicals, Baldwin’s rules of ring closure, Inter and intramolecular
additions of radicals to alkenes and alkynes, Radical chain reactions,
Introduction to polymers and free-radical polymerizations, Named
reactions – Pinacol, acyloin, McMurry, Hoffmann-Lofler-Freytag and
Barton reactions, Use of NBS and tributyl tin hydrides, Ullmann
coupling.
II Organic Photochemistry - Primary photoprocesses. Jablonski diagram, 3, 4
Photoreactions of C=O systems, enes, eneones, dienes and arenes.
Photoisomerisations, Norrish type I and II reactions. Patterno-Buchi
and Barton reactions. Di- -methane and aromatic photo
rearrangements. Photochemical remote functionalisation and hydrogen
abstraction reactions. Introduction to PET, chemi and bioluminescent
reactions. Chemistry of singlet oxygen. Photochemistry in nature.
Photosynthesis. Introduction to organic applied photochemistry and
femtochemistry, photochromism and thermochromism.

III Concerted Reactions - Symmetry properties of MOs. Principle of 2, 4


conservation of orbital symmetry. Pericyclic reactions - theory,
mechanism and stereocourse of electrocyclic reactions, cycloaddition
reactions and sigmatropic rearrangements, 1,3-dipolar cycloadditions,
ene reactions, chelotropic reactions, Sommelet-Hauser, Cope, Claisen
and Mislow-Evans rearrangements, thermal eliminations. Woodward-
Hoffmann selection rules, secondary orbital interactions in [4+2]
cycloadditons, factors affecting rates of cycloaddition reactions.
IV NMR Spectroscopy - Magnetic nuclei with emphasis on 1H and 13C, 5, 6
shielding, de-shielding and chemical shifts, factors affecting chemical
shifts - Field and anisotropic factors, relaxation processes, chemical

26
and magnetic non-equivalence, 1H and 13C NMR scales, Spin-spin
splitting – AX, AX2, AX3, A2X3, AB, ABC and AMX type coupling,
Coupling constants.. Pascals triangle, first order and non-first order
spectra, Karplus curve, Quadrapule broadening, virtual and long-range
coupling, Shift reagents and their role, Decoupling and double
resonance, Off-resonance decoupling, NOE.
Introduction to 2D NMR. Correlation, NOE and quantum correlation
spectroscopy techniques like COSY, HETCOR, HMQC, HMBC,
NOESY and EXCY. Application of DEPT technique, Problems on
spectral interpretation.
V UV-Vis and IR Techniques - UV-VIS spectra of enes, eneones, arenes 5
and conjugated systems. Woodward-Fieser rules, Solvent effect on
absorption spectra. Chiroptical properties – introduction to CD and
ORD, Cotton effect, octant rule, axial haloketone rule. Characteristic
IR bands of functional groups. Factors affecting the IR stretching
frequency – vibrational coupling, hydrogen bonding, electronic,
inductive and field effects, Identification of functional groups and other
structural features by IR.
VI MS in organic structure analysis. EI, CI, SIMS, FAB, ES and MALDI 5, 6
ion production methods. Characteristic EIMS fragmentation modes and
MS rearrangements including McLafferty rearrangement, Spectral
interpretation, structure identification and solving of structural
problems using numerical and spectral data.

REFERENCES
 ROC Norman and JM Coxon, “Principles of Organic Synthesis”, CRC Press, 3rd En, 1993.
 “Fundamentals of Photochemistry” – KK Rohatgi-Mukherjee, New Age International; 2017
 Ian Fleming "Pericyclic Reactions", Oxford University Press, 2015
 Williams, D. H. and Flemming, I. “Spectroscopic Methods in Organic Chemistry”, 5th Edition,
McGraw Hill. 2011
 Kemp, W. “ Organic Spectroscopy” Palgrave, 1991 (2008 reprint)

ADDITIONAL REFERENCES
 Clayden, J., Greeves, N and Warren, S. “Organic Chemistry”, OUP, 2001
 Coxon, J. M. and Holton, B. "Organic Photochemistry", Paperback, 2015
 Kagan, J. “Organic Photochemistry, Principles and Applications”, Paperback, 1993
 KC Majumdar and P. Biswas “Textbook of Pericyclic Reactions” MEDTECH, 2015
 Kalsi, P. S. "Organic Spectroscopy", Wiley Eastern, 2014.
 Pavia, D. L. Lampman, G.M. and Kriz, G. S. “Introduction to Spectroscopy” 3rd Edition,
Brooks/Cole, 2001.
 JR Dyer “Applications of absorption spectroscopy or organic compounds” PHI learning, 2015
 Silverstein, R. M. et sl. “Spectrometric Identification of Organic Compounds” 8th Edn, Wiley.
 Wayne, C. E. and Wayne, R. P. “Photochemistry”, OU Primer 39, OUP.

27
Model Question Paper

SECOND SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-CC-522: ORGANIC CHEMISTRY II

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

21. What is the product formed when CO2H(CH2)8CO2H is treated with sodium in xylene
followed by hydration?
22. Illustrate the polymerization mechanism of styrene.
23. Illustrate Di-pi-methane rearrangement.
24. Provide mechanism for the following conversion:

light

25. Predict the products formed when the following molecules are irradiated (i) (2Z, 4E)-
hexadiene and (ii) (2Z, 4Z, 6E)-octatriene.
26. Depict the cycloaddition of tropone with butadiene.
27. Illustrate the product formed when benzyne undergoes cycloaddition to i) anthracene and
ii) furan.
28. How many signals are present in the broadband decoupled 13CNMR spectrum of i)
catechol (ii) resorcinol and (iii) hydroquinone?
29. A compound shows the following 1HNMR values: δ 9.2 (1H, s), 7.3-7.8 (5H, m), 6.8 (1H,
d), 6.6 (1H, d). Identify the compound. What happens to the 1HNMR if the compound is
reduced?
30. Identify the structure of C8H10O whose NMR spectra has 3 singlets at δ 2.1, 3.7 and 7.1
in the intensity ratio 3:2:5.
31. What is the characteristic feature in the MS of an organic compound containing (i) 3 Cl
atoms and (ii) 2 Br atoms?
32. Determine the absorbance of a solution of an organic dye (0.0007moldm-3) in a cell with
a 2cm pathlength if its absorptivity is 650mol-1dm3cm-1.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

33. How can the following conversion be effected? Give the reagents and mechanism.

28
CHO
R R
HO HO

O O
34. What are the products formed when the following molecules are treated with Bu3SnH and
AIBN
O
Br
i) ii) Br

35. Explain the mechanism of the following reaction.


Me
Ph Me
O + O
N heat
CHO OHC
36. Based on the FMO theory predict and explain the product formation when (2E, 4Z, 6E)-
octatriene electrocyclizes a) thermally and b) photochemically
37. A compound with molecular formula C4H6O2 shows an IR band at 1770 cm-1. The
13
CNMR peaks are at 178, 68, 28 and 22 ppm. The compound is either five-membered or
a four-membered lactone with a side chain. Deduce the correct structure.
38. Arrange the following in the order of increasing IR stretching frequencies i) cyclobutene-
1,2-dione, cyclohex-2-enone, cyclopent – 2-enone and tropone ii) benzophenone, 4-
chloro-benzaldehyde, anisaldehyde and benzaldehyde.
39. What is the intensity ratio of the molecular ion cluster in (i) CH2Br2 and (ii)CH2Cl2?
40. What is the mass of metastable ion produced due to decomposition of fragment ion (m/z:
177) in the sequence: Diethyl phthalate (M+: 222) to (fragment 1)+ (177) to (fragment 2)+
+ CO.

SECTION-C
Answer any 2 questions. Each question carries 8 marks

41. a) Explain the orbital correlation diagram for an electrocyclic reaction.


b) Predict the major product formed from the following pericyclic reactions
[4+4]
N
+ ? SO2
(i) (iii) ?
heat heat

Ph
(ii) N PhN3 S ?
? (iv) heat
heat O

22. a) How can cis-2-butene be differentiated from trans-2-butene using i) IR spectroscopy and
ii) NMR spectroscopy?
b) Depict and explain the 1H-1H COSY spectrum of iso-butyl acetate [4+4]

29
23. a) Identify the structure of the two isomers A and B of molecular formula C8H7BrO2
IR 1H NMR chemical shift
cm-1
Isomer A 1698 2.8, s; 3 sets of Ar H's at 7.2-7.4 (2 sets of soublets), 7.44-7.48 (dd), 7.52-7.6 (dd)
Isomer B 1688 2.6, s; Symmetric aromatic H's at 7.6, d and 7.8, d
b) Explain NOE with an example [4+4]
24. a) Explain why [4+2] cycloaddition is thermally allowed whereas [2+2] is forbidden using
FMO theory.
b) Illustrate the synthesis of i) oxetanes and ii) cyclobutanes by photochemical reactions.

30
1. Semester 2
2. Course Title PHYSICAL CHEMISTRY II
3. Course Code CHE-CC-523
4. Credits 3
5. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Understand and apply approximation methods to solve for many 2-Un;3- CK,PK I,II,III
body problems. Ap
2. Derive the various atomic and diatomic molecular term symbols 4-An CK I, II, III
3. Explain and differentiate molecular orbital and valence bond 3-Ap; CK I, II, III
theories 4-An
4.Explain HartreeFock Theory and semiempiricalHuckel MO treatment 3-Ap CK,PK II, III, IV,
and its application to conjugated molecules VI
5. Understand the principles of the rotational, vibrational, electronic, 2-Un FK,CK I, II
and magnetic resonance spectroscopic techniques
6. Apply the principles of spectroscopy and interpret the data to 2-Un, CK,PK II, III, IV,
understand the structure of compounds 4-An,5- VI
Ev
MODULE COURSE CONTENT CO No.
No
I Many electron atoms- Approximations. Independent particle model. Variational method. 1,2
Theorem and proof. Variational treatment of hydrogen and helium atom. Secular
st nd
determinant. Perturbation method – 1 and 2 order perturbation to energy and wave
function. Application to particle in 1-D box of increasing potential, Helium atom.
self-consistent field method. Pauli’s exclusion principle. Symmetry and antisymmetry
wave functions. Slater determinants. Vector atom model. Spin orbit coupling.
Spectroscopic Term symbols and spectral lines.
II Molecular problems. Born-Oppenheimer approximation. Molecular Orbital Theory. MO 2,3
theory of hydrogen molecule ion. Valence Bond theory (H2). MO theory of H2 and other
homonuclear diatomic molecules. Molecular orbital diagrams, Bond order and stability.
MO theory of simple heterogeneous diatomic molecules like HF, LiH, CO and NO. Defects
in simple MO and VB theories.Semi empirical MO treatment of planar conjugated
molecules. HuckelMO theory and calculation of energy and MO of ethylene, butadiene
and allylic anion and cyclic systems – cyclobutadiene and benezene. Calculation of charge
distribution, bond order and free valency.
III Ab initio methods. Hartree equations and Hartree-Fock equations for molecular 4
problems. Roothaan modification. Hartree Fock Roothan equations.Basis sets andBasis
functions. Slater type orbital (STO) and Gaussian type orbital (GTO). Contracted and
primitive. Basis sets and classification. Minimal, multiple zeta, split-valence, polarized and
diffused. Pople style basis sets. Electron correlation and relativistic effects, Configuration
interaction. Z-matrtix.
IV Spectra of diatomic molecules: Microwave spectroscopy. Rotation of diatomic molecules. 5,6
Rotational spectrum. Intensity of spectral lines. Calculation of internuclear distance.
Nonrigid rotors and centrifugal distortion. Introduction to instrumentation. Infrared
spectroscopy: Rotational spectra of polyatomic molecules. Linear and symmetric top
molecules. Vibrational spectra of harmonic and anharmonic diatomic molecules.
Fundamental and overtones. Determination of force constants. Vibrational rotational
couplings. Different branches of spectrum. Symmetry of vibrational-rotation spectrum.
Vibrational spectra of polyatomic molecules. Normal modes. Classification of vibrations.
Overtones, combination and Fermi resonance. Group frequencies.Introduction to

31
instrumentation and FT IR.
V Raman spectra: Scattering of light. Raman scattering. Polarizability and classical theory of 5,6
Raman spectrum. Quantum theory of Raman spectrum. Rotational and vibrational Raman
spectrum. Introduction to instrumentation. Laser Raman spectrum. Raman spectra of
polyatomic molecules. Complementarity of Raman and IR spectra.Electronic spectra:
Term symbols of molecules. Electronic spectra of diatomic molecules. Vibrational coarse
structure and rotational fine structure of electronic spectrum. Franck-Condon principle.
Herzberg-Teller vibronic coupling, KHD equation, Fermi Golden rule. Types of electronic
transitions. Fortrat diagram. Predissociation. Morse function. Calculation of heat of
dissociation. Introduction to instrumentation.Electronic spectra of polyatomic molecules:
Electronic transitions and absorption frequencies. Effect of conjugation.
VI Resonance spectroscopy: Nuclear spin and interaction with an applied magnetic field. 5,6
Nuclear resonance. Population of energy levels. 1H NMR spectrum. Chemical shift.
Relaxation, Spin-spin coupling, Fine structure; Fourier transform NMR spectroscopy,
Nuclear overhauser effect, NMR spectra of other nuclei. Introduction to instrumentation.
Electron spin in molecules and its interaction with magnetic field. ESR spectrum. The g
factor and its determination. Fine structure and hyperfine structure. Mossbauer
spectroscopy: Doppler effect. Chemical shift. Quadrupole effect.
References:
 th
Levine, I. N., "Quantum Chemistry", 7 Edition, Pearson Education Inc., 2014.
 nd
McQuarrie, D. A., "Quantum Chemistry", 2 Edition,University Science Books, 2008.
 Banwell, C. N.; McCash, E.M., “Fundamentals of Molecular Spectroscopy", 4th Edition, McGraw-Hill, 1999.
 Barrow, G. M., " Introduction to Molecular Spectroscopy", McGraw Hill, 1962.
 Daniels, F. and Alberty, R. A., "Physical Chemistry",4th Edition, Wiley Eastern, 1976.

ADDITIONAL REFERENCES
 Atkins, P. W., "Physical Chemistry", 9th Edition, OUP, 2010.
 Chandra, A. K., "Introduction to Quantum Mechanics", 4th Ed, Tata McGraw-Hill, New Delhi, 2003.
 Prasad, R. K., “Quantum Chemistry”, 4th Edition, New Age International, 2009.
 Drago, R. S., "Physical Methods in Inorganic Chemistry", East West, 2012.
 Moelwyn Hughes, E. A., "Physical Chemistry", 2nd Revised Edition, Pergamon, 1965.

Model Question Paper

SECOND SEMESTER M.Sc. DEGREE EXAMINATION, Month Year


Branch: CHEMISTRY
CHE-CC-523: PHYSICAL CHEMISTRY II
Times: 3 Hours Max. Marks: 60

SECTION- A

Answer any 10 questions. Each question carries 2 marks.

1. Write down the perturbation term in the Hamiltonian of Helium atom.


2. Write down the Slater determinant of Li atom.
3. What is Born-Oppenheimer approximation? Why is it important?
4. Write down the ground state term symbol for a) O2 b) CO
5. Write down the Huckel determinant for benzene and cyclobutadiene.

32
6. Differentiate between ab initio and semiempirical MO treatments.
7. The microwave spectrum of CN shows a series of lines separated by 3.8 cm -1.Calculate the
internuclear distance between C and N.
8. Homonuclear diatomic molecules are IR inactive, but Raman active. Why?
9. What are polarized Raman lines? How is it important in the structure elucidation?
10. What is the significance of Franck Condon principle?
11. What is ‘g factor’? Explain its significance.
12. Which is the commonly used reference standard in 1H NMR? Why is it preferred?

SECTION- B
Answer any 6 questions. Each question carries 4 marks.

13. State and Prove variational theorem.


14. Explain various steps to solve H2 by VB method.
15. Define Coulomb and Exchange integrals. Justify their sign and magnitude.
16. The fundamental and first overtone transitions of NO are centered at 1876 cm-1 and 3724 cm-1
respectively. Calculate the equilibrium vibration frequency and anharmonicity constant.
17. Give a brief note on FTIR.
18. Explain Fortrat diagram.
19. Explain the quantum theory of Raman spectrum.
20. Explain the ESR spectrum of methyl radical.

SECTION- C
Answer any two question. Each question carries 8 marks

21. a) Set up first order perturbation equation for a non-degenerate system


b) Solve this to get the expression for first order correction to energy and wave function.
(3+5)

22. a) Briefly explain the approximations involved in the Hückel MO method.


b) Calculate the delocalization energy of benzene using HMO method. (3+5)

23. a) Write a note on anisotropic effect in 1H NMR.


b) Explain in detail the factors that govern the chemical shift values. (4+4)

24. a) Explain the factors that affect the intensity of spectral lines
b) Distinguish between pure rotational spectrum and vibrational rotational spectrum of molecule.
How are these different from electronic spectrum? (3+5)

33
1. Semester 2
2. Course Title Inorganic Chemistry Lab II
3. Course Code CHE-CC-524
4. Credits 3
5. CO: On completion of the course, students should be able to: TL KL PSO No.
1. Perform colorimetric experiments for the quantitative 3-Ap CK, PK PSO5
determination of various metals 4-An PSO6
2. Perform simple inorganic synthesis and conduct 3-Ap PK, MK PSO4
characterization techniques such as IR, UV-Vis absorption and 4-An PSO5
NMR spectroscopy PSO6
3. Discuss coordination chemistry of Ni complexes 2-Un CK PSO1
4-An PSO2
MOD. COURSE CONTENT CO No.
No
I Colorimetric estimation of Iron after plotting calibration graph. CO1
II Quantitative estimation of Chromium by colorimetry. CO1
III Quantitative estimation of Manganese by colorimetry. CO1
IV Colorimetric estimations of Ti, W and Cu., after plotting calibration graph. CO1
V Synthesis and Characterization of Ni(II) Complexes CO2, CO3
a. The preparation of [Ni(en)3]Cl2 2H2O
b. The preparation of [Ni(NH3)6]Cl2
c. The preparation of [Ni(en)2]Cl2 . 2H2O
VI Synthesis and characterization of tetraphenylporphyrin and its Zn(II) complex CO2
References:
1. Furman and Welcher, "Standard Methods of Inorganic Analysis", Van Nostrand.
2. Kolthoff, I. M. Elving, V. J. and Sandell, “Treatise on Analytical Chemistry”, Interscience.
3. Skoog, D. A. and West, D. M. "Analytical Chemistry: An Introduction", Saunders.
4. Vogel, I. “A Textbook of Quantitative Inorganic Analysis”, Longman.

34
1. Semester 2
2. Course Title ORGANIC CHEMISTRY LAB II
3. Course Code CHE-CC-525
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Set-up organic reactions - single-step and double-step 3-Ap PK I, V
2. Prepare certain heterocyclic compounds I-R, FK, V
3-Ap PK
3. Purify the products by filtration or chromatography 3-Ap PK V
4. Record the melting point of compounds 3-Ap PK V
5. Apply spectroscopic techniques to characterize compounds 3-Ap, FK, IV, VI
4-An CK
6. Record IR and UV data of compounds 3-Ap CK, IV
PK
MODULE COURSE CONTENT CO
No No.
I Preparation of organic compounds by single step reactions – 1, 2
benzoylation, esterification, nitration, sulphonation, halogenation and
hydrolysis
II Preparation of compounds by double-stage synthesis – nitration 1
followed by hydrolysis, bromination followed by hydrolysis etc

III Reactions of carbonyl compounds – aldol condensation – preparation 1, 2


of chalcones and oximes
IV Preparation of heterocyclic compounds - benzimidazoles, thiazoles and 2
N-alkylated isatins.
V Spectral interpretation of organic compounds [simple as well as those 5
prepared in lab as above} using UV-VIS and IR, NMR analysis of
compounds
VI Recording the UV-Vis and IR spectra of synthesized compounds 6

REFERENCES
 Ahluwalia, V. K. and Aggarwal, R. “ Comprehensive Practical Organic Chemistry”, Vol 1 & 2,
Universities Press.
 Furniss, B. S and others, “Vogel’s Textbook of Practical Organic Chemistry”, ELBS.
 Silverstein, R. M. et al., “Spectrometric Identification of Organic Compounds”, 8th Edn, Wiley.

35
1. Semester 2
2. Course Title PHYSICAL CHEMISTRY LAB II
3. Course Code CHE-CC-526
4. Credits 3
6. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Use the viscometer to measure the viscosity of solutions 2-Un; 3-Ap CK,PK IV; V
2. Measure surface tension of liquids 3-Ap CK IV; V
3. Measure the freezing points of mixtures and apply it to study 3-Ap; 5-Ev CK,PK V;VI
depression constant, association and dissociation and eutectic
diagrams
4. Determine the miscibility temperatures to construct the phase 3-Ap;5-Ev CK,PK V; VI
diagram
5. Determine the transition temperature. 3-Ap CK V;VI
6. Understand the principles of lab techniques adopted in physical 2-Un FK V, VII,
Laboratories,monitor, record and present data in a scientific form VIII
MODULE COURSE CONTENT CO No.
No
I Viscosity: Viscosities of liquids and mixtures of liquids. Verification of Kendall’s 1,6
equation and Jones-Dole equation. Viscosity of polymer solutions. Variation of
viscosity with temperature.
II Surface tension: Surface tension and parachor of liquids by differential capillary 2,6
and stalagmometer methods. Variation of surface tension with concentration.
Determination of atomic parachor.
III Cryoscopy: Determination of molar freezing points. Depression constant and 3,6
molecular mass using solid and liquid solvents. Study of dissociation and
association of solutes. Atomicity of substances like sulphur.
IV Phase equilibria I: CST of phenol-water system. Determination of unknown 4,6
concentrations of NaCl, acetic and oxalic acid. Construction of phase diagrams of
unknown mixtures.
V Phase equilibria II: Construction of Two component eutectic diagrams, 3,6
determination of unknown concentration of given mixture. Three component
systems with one pair of partially miscible liquids. Construction of phase diagrams
and tielines.Composition of homogeneous mixtures.
VI Transition temperature: Transition temperature of sodium acetate. Kf of sodium 5,6
acetate. Molecular mass of urea. Transition temperature of sodium thiosulphate.
References:
 Daniels,F. and Mathews,J. H. "Experimental Physical Chemistry", McGraw Hill, 1970.
 Finlay, A. and Kitchener,J. A. "Practical Physical Chemistry", Longman, 1977.
 James,A. M. "Practical Physical Chemistry", Longman, 1981.
 Shoemaker, D. P. and Garland,C. W. "Experiments in Physical Chemistry", McGraw Hill, 1998.

th
Willard,H. H. Merritt , L. L. and Dean,J. A. "Instrumental Methods of Analysis" 7 Edition, CBS Publishers, 2004..
 Viswanathan, B.; Raghavan, P. S. “Practical Physical Chemistry,” Viva Books, 2004.
 YadavJ. B., “Advanced Practical Chemistry”, Krishna Prakashan Media, 2015.

36
1. Semester 2
2. Course Title ADVANCED INORGANIC CHEMISTRY
3. Course Code CHE-DE-527
4. Credits 2
5. CO TL KL PSO No.
On completion of the course, students should be able to:
1. summarize and describe concepts and practices in nuclear 1-R; 2-U FK, 01, 02
/radiation chemistry CK
2. Compare and explain various special techniques for the synthesis 5-E; 2-U FK, 01, 02
of inorganic compounds CK
3. Analyze various inorganic chemistry reactions for the synthesis of 4-An; 5- CK 02, 03
metal complexes E
4. Rationalize the use of spectroscopic techniques IR and NMR for 4-An; 2- CK 01, 02
the characterization of inorganic complexes U
5. Apply their knowledge in spectroscopic methods to elucidate the 3-Ap; 4- CK, 02, 03
structure of inorganic complexes An MK
6. solve problems regarding the structure of various metal 3-Ap; 4- CK 02, 03
complexes using ESR and Mössbauer spectroscopy An
7. Appreciate the photocatalytic ability of metal complexes in solar 2-Un;5- CK 01, 02,
energy conversion E 03
8. Explain and analyze the chemistry and applications of industrial 2-Un; 4- FK, 01, 02
inorganic materials An CK
MODULE COURSE CONTENT CO No.
No
I Nuclear and radiation chemistry: Fission products and fission yield. Neutron capture 1
cross section and critical size. Nuclear fusion reactions and their applications. Neutron
activation analysis, Chemical effects of nuclear transformations. Positron annihilation
and autoradiography. Synthesis of transuranic elements such as Neptunium,
Plutonium, Curium, Berkelium, Einsteinium, Mendelevium, Nobelium, Lawrencium and
elements with atomic numbers 104 to 109. Radiation safety precaution, nuclear waste
disposal. Radiation chemistry of water and aqueous solutions. Measurement of
radiation doses
II Inorganic synthesis: Special techniques such as chemical vacuum line, plasmas, 2, 3
photochemical apparatus and electrolysis. Synthesis of transition metal complexes
involving the following methods: Electron transfer reaction, substitution reaction,
reactions of coordinated ligands, aldol condensation, imine bromination hydrolysis,
substituent exchange reaction, template effect and macrocyclic ligands. Complexes
with interlocking ring ligands. Formation of supramolecular species.
III Inorganic Spectroscopic Methods:Studies of simple inorganic compounds and metal 4, 5
complexes using IR, Raman and NMRSpectroscopy- Metal ligand vibrations, bonding
modes of acetate, nitrate, sulphate and perchlorate and metal atoms. Application of IR
spectroscopy for the identification of these bonding modes. Far IR spectra. Vibrational
spectra of metal carbonyls. Application of NMR spectroscopy for the structural
investigation of diamagnetic metal complexes from chemical shift and spin-spin
coupling.
IV ESR and Mössbauer spectroscopy of coordination compounds: ESR spectra of metal 6
complexes- hyperfine splitting, g values, zero field splitting and Kramers degeneracy.
Application of ESR spectroscopy in the structural investigation of copper(II) and
manganese(II) complexes. Mössbauer spectroscopy- Mössbauer effect, hyperfine

37
interactions, isomer shift, electric quadrupole and magnetic hyperfine interactions.
Application of Mössbauer spectroscopy in the structural study of iron and tin
complexes.
V Inorganic photochemistry: Photochemical laws and kinetics. Photophysical processes. 7
Excited states, ligand field states, charge-transfer states. Fluorescence and
phosphorescence. Photochemical reactions-substitution and redox reactions of Cr(III),
Ru(II) and Ru(III) complexes. Applications-synthesis and catalysis, chemical actinometry
and photochromism. Metal complex sensitizers-electron relay, semiconductor
supported metal oxide systems, solar energy conversions; water photolysis and CO2
reduction. Chlorophyll and light reaction in photosynthesis.
VI Chemistry of Materials:Glasses, ceramics, composites, nanomaterials-preparative 8
procedures. Sol-gel synthesis, glassy state-glass formers and glass modifiers, ceramic
structures, mechanical properties, clay products, refractories- characterizations,
properties and applications. Ultramarines, zeolites and Metal organic frameworks
(MOF); Synthesis structure and applications.
REFERENCES:
 Arnikar, H. J. “Essentials of Nuclear Chemistry”, Wiley Eastern, 1982.
 Cotton, F. A. and Wilkinson, G. “Advanced Inorganic Chemistry”, 6 Edn, Wiley Interscience, New York, 1999.
th

 Emeleus,H. J and Sharpe,A.G. “Modern Aspects of Inorganic Chemistry”, 4th Edn.,ELBS, 1973.
 Huheey, J. E. Keiter, E. A. and Keiter, R. L. “Inorganic Chemistry - Principles of Structure and Reactivity”, 4
th

Edn, HarperCollins, New York., 1993.


 Nakamoto, K. “IR and Raman Spectra of Inorganic and Coordination Complexes, Part A-Theory and
Applications in Inorganic Chemistry”, 6th Edn., John Wiley & sons, 1997.
 Wilkins, R. G. “Kinetics & Mechanism of Reactions of Transition Metal Complexes”, 2 Edn, VCH.
nd

ADDITIONAL REFERENCES
 Porterfield, W. W. “Inorganic Chemistry: A Unified Approach”, Academic Press, 1993
 Goshal,S. N. “Nuclear Physics”, S. Chand and Company, 2006.
 Adamson, W and Fleischauer, P.D. “Concepts of Inorganic Photochemistry”, Wiley, 1975.
 Agarwal, C. V. “Chemistry of Engineering Materials”, 9th Edn., B.S. Pub., 2006.
 Banwell, C. N and McCash, E.M. “Fundamentals of Molecular Spectroscopy”, 4th Edn.,
 Bridson, K. “Inorganic Spectroscopic Methods”, Oxford University Press, 1998.
 Drago, R. S. “Physical Methods in Chemistry”, Saunders College, 1992.
 Purcell, K. F and Kotz, J.C. “Inorganic Chemistry”, Holt-Saunders, 2010.
 Roundhill, D. M. “Photochemistry and Photophysics of Metal Complexes”, Plenum press, 1994.
 Balzani, V and Carassiti, V. “Photochemistry of Coordination Compounds”, Academic Press, 1970.
 Jain, P. C abd Jain, M. “Engineering Chemistry”, 12th Edn., Dhanpat Rai Pub., 2006.
 MacGillyvray, L. R and Lukehart, C. M. “Metal Organic framework materials”, Wiley, 2014
 Mehrotra R. C. and Singh, A. “Organometallic Chemistry: A Unified Approach”, New age international, 2007.
Press, 1994.

38
Model Question Paper

SECOND SEMESTER M.Sc. DEGREE EXAMINATION Month Year


Branch: CHEMISTRY
CHE-CC-527:ADVANCED INORGANIC CHEMISTRY

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. What is nuclear fission energy ?


2. Define neutron capture cross section.
3. Describe a scheme for the synthesis of hexaamminecobalt(III) from cobalt(ii) chloride in
aqueous medium.
4. What are cryptates and cryptands ?
5. Suggest an experimental method to distinguish between terminal and bridging binding
modes of CO ligands in transition metal carbonyl complexes.
6. How can you use NMR spectroscopic technique to identify fluxional behaviour in
transition metal complexes?
7. What is Kramers degeneracy ?
8. Explain how the anisotropy in g value can be used to provide information about the
electronic ground state of transition metal ion complexes.
9. What is photochromism ?
10. How do you explain the intense purple colour of KMnO4 ?
11. Explain the structure of sodalite.
12. What is meant by glass modifier ?

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Phosphorus-32 has a half-life of 14.3 days. What fraction of a sample of phosphorus-32
would remain after 5.5 days ?
14. Discuss different classes of substitution reactions in inorganic chemistry.
15. Explain the effect of macrocyclic ligands in stabilizing transition metal complexes.
16. Illustrate the use of IR spectroscopy in distinguishing the hapticity of cyclopentadienyl
ligand in transition metal complexes.
17. How do you distinguish high and low spin iron complexes using Mössbauer
spectroscopy ?
18. Explain Jablonski diagram with a neat sketch.
19. Explain photochemical redox reaction using Cr(III) complexes as an example.

39
20. Explain the difference between the composite and blend with suitable examples.

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Discuss the chemical vacuum line and plasma technique used in inorganic synthesis.
22. i) Write a note on neutron activation analysis.
ii) Illustrate mutual exclusion principle with suitable transition metal complexes as
examples.
(4 + 4)
23. Discuss the importance of metal complexes in solar energy conversion.
24. i) How do you use ESR spectroscopy in structural determination of manganese(II)
complexes ?
ii) Write a short note on the synthesis, structure and applications of metal
organic frameworks.

(4 + 4)

40
1. Semester 2
2. Course Title ADVANCED ORGANIC CHEMISTRY
3. Course Code CHE-DE-528
4. Credits 2
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Get an overview of supramolecular assemblies and their I-R, FK, I, II
importance 2-Un CK
2. Comprehend the green chemistry principles and how they are being 2-Un, FK, II, III
implemented 3-Ap, CK
4-An
3. Get an introduction to medicinal chemistry and drug action 1-R, FK I, II
2-Un,
4. Understand polymerization mechanisms and processes 2-Un, FK I, II
3-Ap
5. Analyze and estimate functional groups present in oils, milk, starch 4-An FK, III, VI
etc. 5-E CK
MODULE COURSE CONTENT CO No.
No
I Supramolecular Chemistry - Noncovalent interactions: Molecular and 1
chiral recognition, Host-Guest chemistry and inclusion complexes:
crown ethers, cryptands, calixarenes, cyclophanes and cyclodextrins,
Self-Assembly and Self-Organization, Molecular Aggregates: lipid
membranes, nanotubes, micelles and liquid crystals, Fullerene based
supramolecular systems, Dendrimers, Molecular devices: molecular
switches and wires, Molecular recognition in biological systems like
DNA and proteins.
II Chemistry of Biomolecules - DNA replication, Codon and anticodon 1
recognition. Protein biosynthesis, transcription and translation, Genetic
code, DNA sequencing. DNA profiling and the Polymerase Chain
Reaction (PCR).

III Green Chemistry - Background, origin and principles of green 2


chemistry. Atom economy and other metrics of greenness. Examples of
green processes. Solid supports, Supercritical carbon dioxide,
Microwave and sonochemical synthesis. Synthesis using solventless or
alternate media conditions: fluorous and ionic liquid media.
IV Medicinal Chemistry and the Chemistry of the Cell - Introduction to 3
drug discovery and design, drug administration, Drug action –
pharmacokinetic and pharmacodynamic phases, receptor proteins, drug
receptor interaction, drug action, drug selectivity, drug metabolism,
Classification of drugs, Anti-anginal drugs, antihypertensive agents,
antimalarial drugs, aminoquinolines, Antibiotics and analgesics with
examples. Drug stability, Penicillins, tetracyclins and cephalosporins.
Drugs for cancer, AIDS and diabetes, Composition and structural
features of lipids.
V Polymer Chemistry - Classes of polymers. Types and mechanisms of 4
polymerization reactions (free-radical, cationic and anionic). Methods
of molecular mass and size distribution determination. GPC and Light
scattering techniques, Polymer structure and property characterisation.

41
Synthesis of stereoregular polymers. Polymerization techniques. Bulk,
Solution, melt, suspension, emulsion and dispersion techniques, Group
Transfer, metathesis and ring opening polymerization.
Copolymerization. Polymers as supports, reagents and catalysts,
Biodegradable polymers, conducting polymers.
VI Quantitative analysis of organic functional groups - Analysis of oils 5
and fats. Principle of the analysis of milk and starch based food
materials. Organic trace analysis using spectrophotometry and
fluorimetry.

REFERENCES
 Lehn, J. M. “Supramolecular Chemistry – Concepts and Perspectives”, VCH, 1995
 Anastas, P. T. and Warner, J. C. “Green Chemistry: Theory and Practice,” OUP.
 Ahluwalia, V. K and Chopra, M. “Medicinal Chemistry”, Ane Books, 2008.
 Billmayer, F. W. “Textbook of Polymer Science”, 3rd Edn, Wiley. N.Y. 1991.
 Gunzler, H. and Williams, A. Handbook of Analytical Techniques, Vol. 1&2, Wiley VCH

ADDITIONAL REFERENCES
 Vogtle, F. “Supramolecular Chemistry – An introduction ”, Wiley, 1993.
 VK Ahluwalia “Green Chemistry – Environmentally Benign Reactions”, Paperback 2012
 VR Gowarikar “Polymer Science” , New Age International, 2015
 Wilson and Gisvolds.“Text book of Organic, Medicinal and Pharmaceutical Chemistry”, J. B.
Lippincott Williams and Wilkins, 2011
 Lehninger, A. L. Nelson, D. L. Cox, M. M. “Principles of Biochemistry” 5th Edn., W. H. Freeman,
2008
 Holmes, D. J. and Peck, H. “Analytical Biochemistry”, 3rd Edn, Longman, 1998

Model Question Paper

SECOND SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-DE-528ADVANCED ORGANIC CHEMISTRY
Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Suggest a synthesis method for 18-crown-6 and explain one application.


2. How can calixarenes and porphyrins form supramolecular systems?
3. Give the structures of RNA and DNA
4. What is PCR? Explain the important points.
5. Give any two examples for sonochemical synthesis.
6. What are ionic liquids? Illustrate an example of its synthesis and application.
7. What are prodrugs? Give an example.
8. What are the factors affecting the degree of drug absorption?
9. Explain the light scattering method for molecular weight determination of polymers.
10. Give two examples each of i) biodegradable polymer and ii) conducting polymer

42
11. How can the iodine content in a organic compound be analyzed?
12. What are POP’s? Give examples.

SECTION-B
Answer any 6 questions. Each question carries 4 marks
13. Illustrate the self-assembly of i) barbituric acid and 2,4,6-triamino pyrimidine and ii)
bipyridine in presence of Cu(I).
14. How are liquid crystals classified? Give examples.
15. Explain the primary structure determination of a protein.
16. Provide examples of reactions taking place in i) MW conditions and ii) in solid supports
17. Explain the SFE and SFC techniques.
18. What is meant by ADME of a drug? Explain.
19. Explain bulk and emulsion polymerization techniques.
20. How is the lactose content in milk determined?

SECTION-C
Answer any 2 questions. Each question carries 8 marks
21 a) What are the essential features that a molecule should possess to act as a molecular
wire? Give example.
b) Luminescent cryptates of Eu(III) can be used to construct photonic devices. Explain.
22. a) Discuss the principles of green chemistry
b) Discuss any two green chemistry experiments which can be done in a lab.
23. a) Explain group transfer and ring opening polymerization techniques.
b) What are stereoregular polymers and how are they synthesized?
24 a) Explain protein biosynthesis.
b) How can the amount of detergent in a water sample be analyzed and how can it be
removed?

43
1. Semester 2
2. Course Title ADVANCED PHYSICAL CHEMISTRY
3. Course Code CHE-DE-529
4. Credits 2
6. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Explain industrially important metal complex catalyzed 3-Ap CK,PK II, III
reactions
2. Understand the basics of ultrafast reactions 2-un FK I, II
3. Understand various corrosion methods and determine ways to 2-Un; 5-Ev FK,CK I, II, III
control them.
4. Explain and differentiate various energy storage cells 3-Ap; 4-An FK,CK II, III, VI
5. Understand the concepts and theories of photochemical and 2-Un; 3-Ap FK II, III, VI
photophysical process of energy transfer and its applications
6. Understand the basics of computational chemistry for quantum 2Un CK,PK II,III, VI
chemical calculations
MODULE COURSE CONTENT CO No.
No
I Surface area and porosity measurement. Preparation of catalysts, Precursor compound, 1,2
Preactivation and activation process. Basic steps of phase transfer catalyzed reactions,
transfer and intrinsic rates of catalysis.
Metal complex catalyzed reactions. Hydrogenation. Wacker oxidation. Monsanto acetic
acid synthesis. Hydroformylation. Thermal and photochemical Water Gas Shift reactions.
Olefin metathesis. Fischer-Tropsch reaction. Mobil process for the conversion of
methanol to gasoline hydrocarbons. Ultrafast reaction dynamics. Introduction. Ultrafast
lasers. Supersonic beams - pump-probe spectroscopy. Applications.
II Corrosion and its Control:Nernst Theory, Standard Electrode Potential, Galvanic Series, 3
Concentration cell, Types of corrosion: Uniform and Galvanic, Erosion, Crevice, Pitting,
Exfoliation and Selective leaching, Inter-angular Stress, Waterline, Soil, Microbiological.
Theories of corrosion: Acid, Direct Chemical attack, Electrochemical, Corrosion reactions,
Factors affecting corrosion, Protective measures against corrosion, Sacrificial anode, and
impressed current cathode protection.
III Protective Coatings:Paints: Constituents, functions & mechanism of drying. Varnishes 3
and Lacquers; surface preparation for metallic coatings, electroplating (gold) and
electrode less plating (Nickel), anodizing, phosphate coating, powder coating &
antifouling coating. Laser assisted surface engineering, Micro-Arc oxidation, Electro-
spark coating.
IV Electrochemical storage cells: Charging and discharging, storage density, energy density. 4
Different types of batteries: (i) Lead Acid (ii) Nickel-Cadmium, (iii) Zinc manganese
dioxide. Modern batteries: (i) Zinc-Air (ii) Nickel-Metal Hydride, (iii) Lithium battery. Fuel
cells; thermodynamic efficiency, electromotive force of fuel cells: Low temperature fuel
cells: Hydrogen–oxygen fuel cells– alkaline and polymeric membrane types. Basics of
Microbial fuel cells: construction, electrodes used, electron transfer mechanism.
V Advanced Photochemistry:Energy transfer- theories of energy transfer, 5
Photosensitization of organic and inorganic molecules – Singlet oxygen – methods of
singlet oxygen generation and detection – chemistry of singlet oxygen – photodynamic
therapy of cancer. Photoinduced electron transfer (PET) - concepts and theories.
Photochemistry and Photophysics of semiconductors – semiconductor photocatalysis
and applications. Artificial solar energy harvesting- photochemical splitting of water, dye

44
sensitized solar cells.
VI Computational Chemistry:Empirical, Semi empirical and ab initio methods. Hartree-Fock 6
SCF methods. Basis functions- STO and GTO, primitive and contracted functions. Basis
sets. Minimal, split-valence, polarized and diffused, Effective core potential (ECP). Pople
style basis sets and examples. Calculating the number of basis functions for a molecular
calculation. Molecular properties. Mulliken charges. Dipole moments. Geometry.
Molecular orbitals-occupied and virtual. Overlap and overlap population. Specification of
molecular geometry in Cartesian coordinates and internal coordinates. Z-matrix of
molecules H2O, NH3, CH4, eclipsed and staggered ethane. Dummy atoms and ghost
atoms.
References:
 Appleby, A. S. J. and Foulkes, F. K., Fuel cell Hand Book, Von Nostrand Reinhold, 1989.
 Banerjee, S.N., “An Introduction to Corrosion Science and Corrosion Inhibition”, OxonianPress P. Ltd., New
Delhi, 1985.
 Bruce G Gates, “Catalytic Chemistry”, John Wiley & Sons, Inc. USA, 1992
 nd
Cramer, C. J., “Essentials of Computational Chemistry- Theories and Models”, 2 Edition, Wiley, 2004.
 Daniels, F. and Alberty, R. A., "Physical Chemistry",4th Edition, Wiley Eastern, 1976.
 Environmental Management-Vijay Kulkarni&Ramachandran, T. V., Teri Press, New Delhi, 2009
 Farrauto,R. J. and Bartholomew, C.H., “Fundamentals of Industrial Catalytic Processes”, Blackie Academic and
Professional – Chapman and Hall, 1997.
 rd
Jensen, F., “Introduction to Computational Chemistry”, 3 Edition, Wiley, 2017.
 Narayanan, R. andViswanathan, B., Chemical and Electrochemical Energy Systems, Universities Press, 1998.
 Photoinduced Electron Transfer 1-5 (Topics in Current Chemistry) by J.,Ed. Mattay, Springer; 1 edition. 1990-
1993.
 Photoinduced Electron Transfer by Marye Anne Fox and ChanonM., Part A, B. C and D, Elsevier Science
Publishing Company, 1988.
 Sastry, V.S., “Corrosion Inhibitors, Principles & Applications”, V.S. Sastry, John Wiley & Sons,1998.

Model Question Paper

SECOND SEMESTER M.Sc. DEGREE EXAMINATION, Month Year


Branch: CHEMISTRY
CHE-DE-529: ADVANCED PHYSICAL CHEMISTRY
Times: 3 Hours Max. Marks: 60

SECTION- A

Answer any 10 questions. Each question carries 2 marks.

1. Write an example for Grubb’s second generation catalyst.


2. How does the reaction of MeCOOMe with CO under conditions of the Monsanto ethanoic acid
process can lead to ethanoic anhydride.
3. What do you understand by electrochemical series? How is it useful in determination of corrosion of
metals?
4. What is sacrificial anode? Mention its role in control.
5. What is a vehicle or drying oil? Mention their functions.

45
6. What is phosphate coatings and why it is employed?
7. What is meant by electrochemical cell? Explain the functioning of Daniel cell?
8. What is dry cell? Explain.
9. What is singlet oxygen? Write one method for its generation.
10. Discuss the working of a solar cell?
11. What is the difference between 6-31G* and 6-31+G?
12. What are contracted and primitive basis functions?

SECTION- B
Answer any 6questions. Each question carries 4 marks.

13. Explain the mechanism of olefin metathesis reaction.


14. Explain the corrosion of iron by dilute mineral acids.
15. Explain in detail electroless nickel plating.
16. What are fuel cells? Explain the hydrogen-oxygen fuel cell and its advantages.
17. What is photoinduced electron transfer process. Explain Marcus theory to interpret the process in
solution.
18. Explain the applications of semiconductor photocatalysis.
19. Distinguish between semi empirical and ab initio methods in computational chemistry.
20. Differentiate between STO and GTO.

SECTION- C
Answer any two question. Each question carries 8 marks

21. a) Explain the principle and application of femtosecond pump-probe spectroscopy.


b) What are the catalysts employed in olefin metathesis? Discuss. (4+4)

22. a) Explain the term corrosion? Describe the different theories to explain. How can you prevent a
metal from corrosion?
b) What are paints? What are their constituents and uses? (4+4)

23. a) Illustrate photosensitized decomposition of water.


b) Discuss the photodynamic therapy for cancer treatment. (4+4)

24. a) Write the z-matrix of ammonia and staggered ethane


b) What are the basic approximations in HF theory? Explain, how the energy in HF limit differ from
exact energy? (3+5)

46
THIRD SEMESTER

1. Semester 3
2. Course Title INORGANIC CHEMISTRY III
3. Course Code CHE-CC-531
4. Credits 3
5. CO: On completion of the course, students should be able to: TL KL PSO No.
1. Describe the fundamentals of solid state chemistry and X-ray 2-Un, FK PSO1, PSO3
diffraction 4-An
2. Explain and compare solid properties based various binding forces 2-Un, FK, PSO1, PSO3
and imperfections in solids 4-An CK
3. Describe and apply the basics of electrical and magnetic properties 2-Un, FK, PSO1, PSO3
of solids 3-Ap, CK
4-An
4. Examine and correlate the solid state properties with real life 2-Un, FK, PSO1, PSO2
materials 3-AP CK
5. Get an insight about the chemistry of open and closed structure 2-Un, FK PSO1, PSO3
compounds of important non-metallic elements 4-An
6. Describe and examine the structure and properties of various 2-Un, FK, PSO1, PSO3
metallic clusters 4-An CK
MOD COURSE CONTENT CO No.
No
I Introduction to Solid State: Crystal systems and lattice types. Bravais lattices. CO1
Crystal symmetry. Point groups and space groups. Miller indices. Reciprocal
lattice concept. Close packed structures: BCC, FCC and HCP. Voids.
Coordination number. X Ray diffraction by crystals: Functions of crystals.
Transmission and reflection grating. Braggs equation. Diffraction methods.
Powder, rotating crystal, oscillation and Weisenberg methods. Indexing and
determination of lattice type and unit cell dimensions of cubic crystals.
Structure factor. Crystal defects: Point, line and plane defects.
II Solid State Theories and Properties: Binding forces in solids: Ionic bonding and CO2,CO3,CO4
potential energy field. Lattice energy. Born theory and Born Haber cycle.
Molecular, ionic, covalent, metallic and hydrogen bonded crystals. Free
electron theory and band theory of solids. Conductors, insulators and
semiconductors. Mobility of charge carriers. Hall effect. Electrons and holes.
Imperfections and nonstoichiometry (oxides and sulphides). Techniques of
introducing imperfections in solids.Electrical properties of solids: Conductivity
of pure metals. Superconductivity. Photoconductivity. Photovoltaic effect.
Dielectric properties. Piezoelectricity and ferroelectricity. Magnetic properties
of solids: Diamagnetism, paramagnetism, ferromagnetism, ferrimagnetism and
antiferromagnetism. Lasers and their applications.
III Inorganic nanomaterials and applications: Popular and scientific perspective CO5
of nanotechnology; Fabrication of nanomaterials-top-down and bottom-up
methods; Different types of nanostructures- 0D, 1D and 2D materials-
nanoparticles, nanorods, nanocombs, nanotubes, nanowires and quantum
dots, semiconductor nanoparticles; Carbon based nanomaterials and
applications-Fullerene, graphene, carbon nanotubes and
diamondoidnanomaterials; Nonocomposites- natural, organic polymer, metal
and ceramic nanocomposite; Nanomaterials in various applications-Magnetic
nanoparticle for information storage applications, Light-emitting devices based
on direct band gap semiconductor nanoparticles. Nanomaterials for energy

47
applications-fuel cell, photovoltaic and rechargeable batteries. Nanometerials
in biomedical applications.
IV Structures of Sulphur, Nitrogen, Phosphorus and Silicone Compounds: CO6
Sulphur Nitrogen compounds: Tetrasulphurtetranitride, disulphurdinitride and
polythiazyl. SxNy compounds. S-N cations and anions. Other S-N compounds.
Sulphur phosphorus compounds: Molecular sulphides such as P 4S3, P4S7, P4S9
and P4S10. Phosphorus-nitrogen compounds: Phosphazines. Cyclo and linear
phosphazines. Other P-N compounds. Silanes, silicon halides, silicates;
Classification and structure, silicones.
V Structure of Boron Compounds: Boron hydrides: Reactions of diborane, and CO6
its structure and bonding. Polyhedral boranes: Preparation, properties,
structure and bonding. The topological approach to boron hydride structure.
Styx numbers. Wade’s rules. Carboranes: Closo, nido and arachnocarboranes.
Metalloboranes and metallocarboranes. Organoboron compounds and
hydroboration. Boron-nitrogen compounds: Borazine, substituted borazines
and boron nitride.
VI Other Metal clusters: Factors favouring metal-metal bonds, Dinuclear CO7
compounds of Re, Cu and Cr, metal-metal multiple bonding in (Re2X8)2-
trinuclear clusters, tetranuclear clusters, hexanuclear clusters. Carbonyl
clusters-LNCCS and HNCCS, Isoelectronic and isolobal analogy, Wade-Mingos
rules, cluster valence electrons. Polyatomic zintl anion and cations. Infinite
metal chains. Isopoly acids of vanadium, molybdenum and tungsten.
Heteropoly acids of Mo and W.
References:
1. Adams, D, M. Inorganic Solids: An Introduction to Concepts in Solid State Structural
2. Azaroff, L. V. "Introduction to Solids", McGraw Hill.
3. Chakrabarty, D. K. “Solid State Chemistry,” New Age Pub., 2010.
4. Cotton, F. A. and Wilkinson, G. “Advanced Inorganic Chemistry”, 6th Edn, Wiley
5. Galway, A. K"Chemistry of Solids", Chapman Hall.
6. Huheey, J. E. Keiter, E. A. and Keiter, R. L. “Inorganic Chemistry - Principles of Interscience, New York, 1999.
7. Phillips, F. C. “An Introduction to Crystallography”, Longman.
8. West, A. R. "Solid State Chemistry and its Applications", Wiley.
9. Atkins, P. W. and Shriver, D. F. “Inorganic Chemistry”, 5th Edn, OUP, 2009.
10. Douglas, B. E. McDanial, D. H. and Alexander, J. J. “Concepts and Models of Inorganic Chemistry”, 3rd Edn, John
Wiley, 2001.
11. L. H. Gabor, H. F. Tibbals, J. Dutta, J. J.Moore, Intoduction to nanoscience and nanotechnology, CRC press, 2009.
12. M. S. RamachandraRao and S. Singh, Nanoscience and nanotechnology: Fundamentals to frontiers, Wiley, 2014.

Additional references
13. Emeleus, H. J. Sharpe, A. G. “Modern Aspects of Inorganic Chemistry”, 4th Edn., ELBS, 1973.
14. Holleman, A. F. and Wiberg, E. “Inorganic Chemistry”, Academic press, 2001.
15. Kittel, C. “Introduction to Solid State Physics”, Wiley.
16. Lee, J. D. “Concise Inorganic Chemistry,” 4th Edn., Wiley-India, 2008.
17. Purcell, K.FandKotz, J. C. “Inorganic Chemistry,” Holt-Saunders, 2010.

48
Model Question Paper

THIRD SEMESTER M.Sc. DEGREE EXAMINATION Month Year


Branch: CHEMISTRY
CHE-CC-531: INORGANIC CHEMISTRY III

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Explain the basis for classification of lattices into 7 crystal systems and 14 Bravais
lattices.
2. Calculate the number of atom in a unit cell of BCC and FCC crystal structure.
3. Discuss the defect structure in non-stoichiometric sulphides.
4. What are the similarities and differences between ferrimagnetism and
antiferromagnetism ?
5. What is meant by a 2D nanomaterial ? Give example.
6. Explain with example ‘quantum confinement’.
7. Discuss the structure of S4N4.
8. Describe the structure of P4S9 and P4S10.
9. Find styx numbers forB6H10.
10. Even though borazine is isoelectronic with benzene, borazine is far more reactive than
benzene. Why ?
11. Predict the number of metal-metal bonds in Co2(CO)8.
12. Establish the isolobal analogy between CH3 and Mn(CO)5.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Differentiate between FCC and HCP close packed structures.


14. What are intrinsic and extrinsic semiconductors ?
15. What is superconductivity and critical transition temperature ?
16. Explain with example ‘bottom-up’ approach of nanomaerial synthesis.
17. Discuss the bonding and aromaticity in cyclic phosphazenes.
18. Differentiate closo and nido carboranes with examples.
19. Compare the stability of o- and p- Dicarbadodecarborane.
20. Discuss the different types of bonding modes of carbonyl ligands in LNCCs.

49
SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Differentiate between conductors, insulators and semiconductors based on band theory of
solids.
22. i) Derive Bragg’s equation.
ii) Discuss about the classification of silicates based on their structures.
(4 + 4)

23. Discuss the energy and biomedical applications of nanomaterials.

24. i) Write a note on the application of Wade’s rules in predicting the structures of boranes.

ii) Discuss the bonding in [Re2Cl8]2- .

(4 + 4)

50
1. Semester 3
2. Course Title ORGANIC CHEMISTRY III
3. Course Code CHE-CC-532
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Use various reagents and organic reactions in a logical manner for 1-R, FK, I, II
synthesis of heterocycles and carbocycles 3-Ap CK
2. Use retrosynthetic method for the logical dissection of complex 4-An, FK, I, III
organic molecules and devise synthetic methods 5-E, CK,
6-C MK
3. Choose appropriate oxidation/reduction reagent as needed for the 3-Ap, FK, II, III,
substrate 4-An CK VI
4. Identify the class of natural product and predict the biosynthetic 1-R, FK II, III
pathway 4-An,
6-C
5. Elucidate the structure of some natural products by retrosynthesis 3-Ap, FK, I, VI
and chemical degradation 4-An CK
6. Comprehend the chemistry of amino acids, nucleic acids, proteins 1-R, FK, I, II
and peptides 2-Un CK
MODULE COURSE CONTENT CO
No No.
I Construction of Carbocyclic and Heterocyclic Rings - Importance of 1
heterocyclic compounds, Structure and aromaticity of heterocycles,
Trivial and Systematic Hantzsch Widman Nomenclature of
heterocyclic compounds, Different methods of ring synthesis, Three
and four membered heterocycles, Named reactions for synthesis of
furan, pyrrole, thiophene, pyridine, indole, quinoline and isoquinoline
including Paal-Knorr, Feist-Benary, Fischer indole, Hantzsch, Skraup,
Pictet-Spengler and Bischler-Napieralski methods, Electrophilic and
nucleophilic substitutions of 5-membered, 6-membered, indole,
quinoline and isoquinoline rings, Heterocycles with more than one
heteroatom – synthesis and reactivity. Pauson-Khand reaction, Volhardt
reaction, Bergman cyclization, Nazarov cyclization, Olefin metathesis.
II Organic Synthetic Strategies - Introduction to retrosynthetic analysis. 1, 2
Linear and convergent synthesis, Synthons, functional group
interconversions (FGI), Role of protecting groups in organic synthesis,
Enolate and enamine alkylation reactions including Stork-enamine
reaction, Dipole inversion - Umpolung. Organometallic reagents like
Grignard, alkyl lithium and Gilman Reagents and their utility,
Organocuprates, DABCO and Baylis-Hilman reaction, Role of
palladium in organic synthesis, Heck, Sonogashira, Suzuki, Stille and
Negishi coupling reactions. Glaser coupling, Tebbe olefination, Sakurai
reaction, Brook rearrangement, Mitsunobu reaction, PPh3-CBr4
reagent

III Reagents for oxidation - Oxidations using manganese and chromium 3


reagents, PCC, PDC Collins and Jones reagents, Etard reaction, Use of
SeO2, MnO2, Ag2CO3 and lead tetraacetate, DMSO based reagents -

51
Swern oxidation, Oppenauer oxidation. Oxidation of alkenes - OsO4,
RuO4, HIO4, ozone and peracids. Sharpless asymmetric epoxidation,
Woodward and Prevost hydroxylations, Dehydrogenation to aromatic
compounds. Baeyer-Villiger oxidation, Dakin reaction.
IV Reagents for reduction - Catalytic hydrogenation and stereochemistry. 3
Hydrogenation catalysts and their selectivity. Adam’s catalyst,
Rosenmund reduction, Lindlar catalyst, Wilkinson’s catalyst,
Homogeneous hydrogenations. Fe, Zn, Na and Li reductions.
Dissolving metal reductions – Clemmenson reduction, metal-alcohol
reductions, Birch reduction, Hydride transfer reductions – MPV
reduction, Reduction using NaBH4, LAH, LAH-AlCl3, DIBAL-H and
NaCNBH3, selectrides. Reductions using borane reagents,
hydroboration, Luche reduction, Wolff Kishner and diimide
reductions..
V Natural Products Chemistry - Classification, Isolation, identification, 4, 5
typical examples and structures of secondary metabolites - Alkaloids,
Terpenoids, Steroids, Prostaglandins, Coumarins and flavones.
Degradation methods for structural elucidation – Hoffmann and Emde
methods, examples of alkaloids, Total synthesis of reserpine,
Classification of terpenes, Cationic rearrangements and formation of
cyclic terpenes, Structural elucidation of santonin, Structure and
-carotene and ascorbic acid. Synthesis of
Vitamin C from glucose, Biosynthesis of fatty acids and polyketides by
acetate pathway, monoterpenes by mevalonic acid pathway and
alkaloids by shikimic acid pathway, biosynthesis of higher terpenes and
steroids. Structure of cholesterol and other important steroids, Barbier
Wielander degradation and Blanc rule
VI Chemistry of nucleic acids and proteins - Amino acids, proteins and 6
peptides: Structures and synthesis of amino acids – Strecker synthesis,
Azlactone synthesis and enantioselective synthesis. Reactions of amino
acids due to the NH2 group, COOH group and its reaction with
ninhydrin, Structure of proteins, Introduction to enzyme and co-
enzymes, structure and relevance of NAD, chymotrypsin, pyridoxal and
thiamine, Peptide bond formation methods, amino and carboxy
protection in SPPS. ADP and ATP. Automated polypeptide and
oligonucleotide synthesis. Structure of polysaccharides including
starch, cellulose, glycogen and chitin.

REFERENCES
 Thomas L. Gilchrist “Heterocyclic Chemistry” Pearson, 2013
 P. S. Kalsi “Organic Synthesis through Disconnection Approach” MEDTEC, 2014
 Carruthers, W. “Some Modern Methods of Organic Synthesis”, Cambridge University Press,
2004
 Hanson, J. R. “Natural Products: Secondary Metabolites”, RSC
 Mann, J and others, “Natural Products: Chemistry and Biological Significance”. Longman 2006

ADDITIONAL REFERENCES
 Harbourne, J. B. “Phytochemical Methods” Chapman Hall. 1998
 Warren, S. “Organic Synthesis: The Disconnection Approach”, John Wiley, 2004.
 Hanson, J. R “Organic Synthetic Methods” RSC , 2002.

52
 Norman, R. O. C. and Coxon, A. "Modern Synthetic Reactions", Chapman Hall, 1993
 Mackie, R. K., Smith, D. M. and Aitken, R. A. “Guidebook to Organic Synthesis”, 3 Edn,
Longman.1990
 Krishnaswamy, N. K. “The Chemistry of Natural Products,” Universities Press 2010
 Mann, J. “Chemical Aspects of Biosynthesis”, Oxford primer 20, OUP.1994
 Simmonds, R. J. "Chemistry of Biomolecules", RSC. 1992
 Smith, M. B. "Organic Synthesis", 2 Edn, McGraw Hill. 1994.

Model Question Paper

THIRD SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-CC-532 : ORGANIC CHEMISTRY III

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions.Each question carries 2 marks

1. Illustrate mechanism for the conversion of pyrrole to 3-chloro pyridine.


2. Illustrate the product formed when 2-ethoxy-1,4-pentadiene-3-one is treated with
aluminium chloride at room temperature in acetonitrile.
3. Explain the mechanism of the reaction

4. Illustrate the retrosynthetic analysis for paracetamol.


5. How do you convert 2-butyne to (i) cis-2-butene and (ii) trans-2-butene
6. What product is formed when trans-2-butene is treated with iodine and silver acetate
under anhydrous conditions?
7. An aldehyde can be coupled with ethyl acrylate in presence of DMAP. Illustrate the
reaction with mechanism.
8. What reagents are used for conversion of i) ethyl cinnamate to cinnamyl alcohol and ii)
ethyl benzoate to benzaldehyde?
9. Suggest and illustrate a method to convert bromo benzene to biphenyl.
10. How are fatty acids biosynthesized in living cells?
11. Illustrate formation of shikimic acid in cells.
12. Depict the Strecker synthesis of aminoacids.

SECTION-B
Answer any 6 questions. Each question carries 4 marks
13. What reagents are required to convert cyclohexanone to i) cyclohexane-1,2-dione ii)
cyclohexane iii) cyclohexanol iv) cyclohexyl amine?

53
14. Illustrate a method each for the synthesis of indole and isoquinoline
15. What reagents are required for the following conversions?
O O
O
?

?
O O

16. Give a retrosynthetic analysis and suggest a synthetic strategy for the following
molecules
O
O
and

O O
O

17. Illustrate biosynthesis of monoterpene.


18. Explain the secondary and tertiary structure of proteins.
19. Explain Barbier Wielander degradation and Blanc rule
20. Predict the product formed when isoquinoline is treated with lithium in liquid ammonia.

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Predict the product formed i) dibenzoyl methane reacts with hydroxylamine and ii) N-
chloro-N-methylpentamine is exposed to light in acid medium.
22. Illustrate i) Mitsunobu reaction ii) Glaser coupling iii) Heck reaction and iv) Suzuki
polymerization.
23. What products are formed in the following cases
O
O i) LAH
CN
a) ii) HCl (aq)
iii) NaBH3CN, TsOH, heat

i) Mg ii) CO2
b)
iii) H3O+
iv) (COCl)2 , Et3N
CH2Br
24. Illustrate the retrosynthetic approach and major synthetic strategies adopted for synthesis
of reserpine by Woodward.

54
1. Semester 3
2. Course Title PHYSICAL CHEMISTRY III
3. Course Code CHE-CC-533
4. Credits 3
5. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Understand and apply the laws of thermodynamics and 2-Un;3- CK,PK I, II, III
thermodynamics of irreversible process Ap
2. Explain partition functions and its relationship with thermodynamic 3-Ap; CK II,III, VI
properties 5-Ev
3. Explain and differentiate Maxwell-Boltzmann, Bose-Einstein, and 3-Ap; CK II, III
Fermi-Dirac Statistics 4-An
4. Explain the kinetics of unimolecular, chain and fast reactions. 2-Un CK,PK I,II
5. Understand the theories of reaction rates 2-Un FK,CK I, II
6. Explain the mechanism and theories of homogeneous and 2-Un CK I, II
heterogeneous catalysis
7. Understand and explain the concepts and theories of electrolytes 2-Un; FK,CK I, II, III
and electrodes 3-Ap
MODULE COURSE CONTENT CO No.
No
I First and second laws of thermodynamics. Thermodynamic criteria for equilibrium and 1
spontaneity. The Clausius inequality, Maxwell relations. The third law of
thermodynamics. Need for the third law. Nernst heat theorem. Apparent exceptions to
third law. Applications of third law. Thermodynamics of irreversible processes: Simple
examples of irreversible processes. General theory of nonequilibrium processes. Entropy
production. The phenomenological relations. Onsager reciprocal relations. Application
to the theory of diffusion, thermal diffusion, thermoosmosis and thermomolecular
pressure difference. Electrokinetic effects. The Glansdorf-Pregogine equation.
II Statistical thermodynamics: Mechanical description of molecular systems. 2
Thermodynamic property and entropy. Microstates. Canonical and grand canonical
ensembles. Equation of state for ideal quantum gases. Maxwell-Boltzman distribution.
The partition functions. Partition function for free linear motion, for free motion in a
shared space, for linear harmonic vibration. Complex partition functions and partition
functions for particles in different force fields. Langevins partition function and its use for
the determination of dipole moments. Electrostatic energies. Molecular partition
functions. Translational, rotational, vibrational and electronic partition functions. Total
partition functions. Partition functions and thermodynamic properties. Heat capacity of
gases. Equipartition principle and quantum theory of heat capacity.
III Quantum statistics: Bose-Einstein statistics. Examples of particles. Theory of 3
paramagnetism. Bose-Einstein condensation. Liquid helium. Super cooled liquid.
Fermi-Dirac statistics. Thermionic emission. Relations between Maxwell-Boltzman,
Bose-Einstein and Fermi-Dirac statistics. Heat capacity of solids. The vibrational
properties of solids. Einstein theory of heat capacity. The spectrum of normal modes.
The Debye theory. The electronic specific heat. Structure of liquids, X-ray diffraction
studies, Short range order, radial distribution function, configurational partition function
for liquids. Theories of liquids state. Free space and van der Waals theories. Lennard-
Jones theory of melting. Specific heats and communal entropy of liquids.
IV Order and molecularity of reactions. Time dependency of order. Complex reactions: 4,5
Reversible, consecutive, concurrent and branching reactions. Free radical and chain

55
reactions. Steady state treatment. Reactions like H 2-Cl2 and H2-Br2. Decomposition of
ethane, acetaldehyde and N2O5. Rice-Herzfeld mechanism. Unimolecular reaction.
Lindemann treatment. Semenoff-Hinshelword mechanism of chain reactions and
explosion. Kinetics of fast reactions: Relaxation method. Relaxation spectrometry. Flow
method, Stopped-flow technique. Shock method. Pulse method. Flash photolysis. Factors
influencing reaction rates in solution. Salt effects. Curtin-Hammett equation, kinetic
isotope effect.
Theories of reaction rates. Arrhenius equation, Collision theory, potential energy
surfaces and reaction coordinate, TransitionState theory, comparative study of the
theories. Kinetics of reactions in solution. Diffusion controlled reactions. Ionic reactions
and effect of ionic strength, Effect of solvents, effects of pressure on velocity of gas
reactions.
V Catalysis: Mechanism and theories of homogeneous and heterogeneous catalysis. 6
Acid-base catalysis. Skrabal diagram, Bronsted catalysis law, prototropic and protolytic
mechanisms, acidity function. Enzyme catalysis. Michaelis-Menton equation, effect of pH
and temperature on enzyme catalysis. Mechanism of heterogeneous catalysis-
Unimolecular and Bimolecular surface reactions. Langmuir-Hinshelwood mechanism.
Introduction to photochemistry: Laws of photochemistry. Quantum yield. Radiative and
non-radiative transitions. Fluorescence and phosphorescence. Intensity and
concentration. Fluorescence indicators. Quenching of fluorescence. Chemiluminescence.
Explosion reaction. Kinetics of photochemical reaction of H 2and Cl2, and H2and Br2.
VI Ionic activity. Ion-solvent interaction. Strong electrolytes. Ion transport. Debye-Huckel 7
theory of strong electrolytes, Debye-Huckel limiting law. Mean ionic activity coefficient.
Debye-Huckel- Onsagar equation and its derivation. Debye-Falkenhagen effect. Wein
effect.
Types of electrodes. Electrochemical cells. Liquid junction potential and its
determination. Evaluation of thermodynamic properties and activities. Electrical double
layer, and its various models. Electrode-electrolyte interface. Electrokinetic phenomena.
Current-potential curves. Over potential and its theories. Butler-Volmer equation. Tafel
and Nernst equations. Corrosion and methods for prevention. Porbaux diagram and
Evans diagram. Introduction to polarography, cyclic voltammetry. Theory and working of
Fuel Cells.
References:
 Engel T. and Reid, P. Thermodynamics, Statistical Thermodynamics, & Kinetics, 3rd edition, 2013, Pearson
Education.
 Lakowicz, J. R. Principles of Fluorescence Spectroscopy, 3rd edition, 2006, Springer.
 Houston, P. A., "Chemical Kinetics and Reaction Dynamics", Dover, 2006.
 Panchenkov, G. M. and Labadev, V.P., "Chemical Kinetics and Catalysis", MIR Publishing.
 Laidler, K. J. “Chemical Kinetics” 3rd Edition, Prentice Hall, 1987.
 rd
Moore, J. W. and Pearson, R. G. “Kinetics and Mechanism”, 3 edition, 1981, John Wiley and Sons.
 Bokris, J. O. M.; Reddy, A. K. N., “Modern Electrochemistry”, Wiley-Interscience, 1972.
 Glasstone, S., “Introduction to Electrochemistry”, East West Press Pvt Ltd. 1965.

ADDITIONAL REFERENCES
 Daniels, F. and Alberty, R. A., "Physical Chemistry",4th Edition, Wiley Eastern, 1976.
 Atkins, P. W., "Physical Chemistry", 9th Edition, OUP, 2010.
 Berry, R. S.; Rice, S. A. and Ross, J. “Physical Chemistry”, Oxford University Press, Oxford, 2000.
 Sears, F. W., “Introduction to Thermodynamics, Kinetic Theory of Gases and Statistical mechanics”, 2nd
Edition, Addison Wesley, 1972.

56
Model Question Paper

THIRD SEMESTER M.Sc. DEGREE EXAMINATION, Month Year


Branch: CHEMISTRY
CHE-CC-533: PHYSICAL CHEMISTRY III
Times: 3 Hours Max. Marks: 60

SECTION- A

Answer any 10 questions. Each question carries 2 marks.

1. Define active transport. Explain its significance.


2. State and explain Onsager reciprocal relations.
3. Distinguish between microstate and macrostate.
4. Show that molecular partition function is the product of the partition functions for various degrees
of freedom.
5. Compare the free space and van der waals theories of liquid state.
6. Calculate the pressure and the energy of a 3D non-interacting Boson gas below its BEC critical
temperature?
7. Explain primary salt effect.
8. Radioactivity of a sample (z=22) decreases 90% after 10 years. What will be the half life of the
sample.
9. What is the effect of pH on the rate of an enzyme catalyzed reactions.
10. Differentiate between inter system crossing and internal conversion.
11. Calculate the thickness of ionic atmosphere in 0.01 molal aqueous KCl at 25oC. Dielectric constant of
water is 78.5.
12. Distinguish between inner and outer Helmholtz plane.

SECTION- B
Answer any 6 questions. Each question carries 4 marks.

13. a) Define phenomenological coefficient. Show that direct coefficients always dominate indirect
coefficients.
14. Use third law of thermodynamics, show that absolute zero of temperature is unattainable.
15. Explain the term dilute system. Show that all particles follow Maxwell-Boltzmann statistics under
dilute system conditions.
16. Calculate the heat capacity of diamond at 1000 K. Its characteristic temperature is 1860 K.
17. Explain Lennard Jones theory of melting.
18. Derive the distribution law for velocity of gases in two dimensions.
19. Give the steady state treatment for the reaction H2+Br2 ---> 2HBr
H 2( g ) HCl
20. The emf of the cell Pt AgCl ( S ) Ag was found to be 0.3524 V at 25oC. Calculate the
1b 0.01m

activity coefficient of 0.01m HCl. The standard electrode potential of Cl AgCl ( S ) Ag is 0.2224
V.

57
SECTION- C
Answer any two question. Each question carries 8 marks

21. a) Rationalize thermal osmosis and thermal diffusion using irreversible thermodynamics.
b) Discuss briefly Bose-Einstein condensation. (4+4)

22. a) Explain the Lindemann theory for unimolecular reactions.


b) Give the kinetics for the following reaction 2H2 (g)+O2 (g) ---> 2H2O (g) (4+4)

23. a) Compare the postulates of Maxwell-Boltzmann and Fermi-Dirac statistics.


b)Derive Butler-Volmer equation. Discuss. (4+4)

24. a) Discuss the application of Porbaux diagram in predicting the stability of metals.

b) Provide a comparison of the free space and vander Waals theories of liquid state.

(4+4)

58
1. Semester 3
2. Course Title Inorganic Chemistry Lab III
3. Course Code CHE-CC-534
4. Credits 3
5. CO: On completion of the course, students should be able to: TL KL PSO No.
1. Implement the analytical techniques learned earlier to the real cases 3-AP CK, PSO4,
5-E PK PSO5
MK PSO6
2. Describe and execute ion-exchange separation technique 2-Un CK, PSO4,
4-An PK PSO5
MK PSO6
3. Execute inorganic synthesis of model coordination complexes 4-An PK PSO5
5-E PSO6
4. Interpret and compare the electronic properties of complexes based 3-Ap PK, PSO3
on the given experimental results 4-An MK PSO4
5-E PSO5
5. Describe and operate analytical and spectroscopic tools to 3-AP PK, PSO4
characterize and analyse various inorganic complexes 4-An MK PSO5
5-E PSO6
MOD. COURSE CONTENT CO No.
No
I Analysis of some typical ores: Carbonate ore, sulfate ore, ilmenite and CO1
monazite.
II Analysis of fertilizers: Estimation of nitrogen in ammonium compounds. NPK CO1
estimations in synthetic fertilizers
III Ion exchange separation of binary mixtures: Zn & Mg and Co & Ni. CO2
IV Synthesis of [Ti(urea)6]I3: An air stable d1 Complex. Compare the electronic CO3, CO4,
3+
property with [Ti(H2O)6] CO5
V Preparation of various transition metal complexes CO3
VI Characterizations of prepared metal complexes by UV-VIS, IR, magnetic CO4, CO5
susceptibility and electrical conductivity
References:
1. Drago, R. S. "Physical Methods in Inorganic Chemistry", Affiliated East West.
2. Furman and Welcher, "Standard Methods of Inorganic Analysis", Van Nostrand.
3. Kolthoff, I. M. and Strenger, "Volumetric Analysis", Interscience.
4. Kolthoff, I. M., Elving, V. J. and Sandell, "Treatise on Analytical Chemistry", Interscience.
5. Palmer, W. G. "Experimental Inorganic Chemistry", CUP.
6. Schoder, W. R. and Powell, A. R. "Analysis of Minerals and Ores of Rare Elements".
7. Weining, I. and Schoder, W. P. "Technical Methods of Ore Analysis".

59
1. Semester 3
2. Course Title ORGANIC CHEMISTRY LAB III
3. Course Code CHE-CC-535
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. To estimate the various functional groups present in organic 3-Ap, CK, II, III, V
molecules 4-An PK
2. To apply volumetry for organic analysis 3-Ap FK, V
PK
3. To apply UV-Vis spectrophotometry to analyze certain functional 3-Ap, CK, III, IV
groups PK
MODULE COURSE CONTENT CO No.
No
I Estimation of esters and acids using acid - base titration method. 1, 2
II Estimation of reducing sugars by using freshly prepared Fehling\s 1, 2
solution

III Estimation of phenols, amines and ketones using iodometric titration 1, 2


method
IV Estimation of acid value, iodine value and sap value of oils 1, 2
V Spectrophotometric estimation of total ascorbic acid content in various 3
fruits and vegetables
VI Spectrophotometric estimation of glucose 3

REFERENCES
 Agarwala, A. C. and Sharma, R. M. "A Laboratory Manual of Milk Inspection", Asia Publishing
 Ahluwalia, V. K. and Aggarwal, R. “Comprehensive Practical Organic Chemistry”, Vol 1 & 2,
Universities Press.
 Vishnoi, A. K. “Advanced Practical Organic Chemistry” Vikas Publishing, 2009

60
1. Semester 3
2. Course Title PHYSICAL CHEMISTRY LAB III
3. Course Code CHE-CC-536
4. Credits 3
5. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Use conductometer to perform conductometric titrations, and to 2-Un; 3- CK,PK IV; V; VI
measure equivalent conductance Ap
2. Perform potentiometric titrations 3-Ap CK,PK IV; V; VI
3. Perform polarographic estimations 3-Ap; 5- CK,PK IV; V;VI
Ev
4. Perform flame photometry or Karl-Fischertitrator estimations 3-Ap;5- CK,PK V; VI
Ev
5. Create a program in C++ or calculate simple properties of 3-Ap; 6-
PK,MK V;VI
molecules employingsemiempirical MOT program. Cr
6. Understand the basic principles of lab techniques adopted in 2-Un FK V, VII,
physical VIII
Laboratories,monitor, record and present data in a scientific form
MODULE COURSE CONTENT CO No.
No
I Conductance: Verification of Onsagar equation. Solubility of sparingly soluble substances. 1,6
Oswald’s dilution law. Basicity of acids. Dissociation constants of acids and bases.
Conductometric titrations involving acid-base and precipitation reactions. Equivalent
conductance of solutions of strong electrolytes and weak electrolytes.
II Potentiometry: Single electrode potentials of hydrogen and glass electrodes. Quinhydrone 2,6
electrode. Potentiometric titrations involving acid-base, redox and precipitation reactions.
pH of buffer solutions. Solubility of AgCl. Determination of dissociation constant.
III Polarography: Polarographic estimation of cadmium, zinc and lead. Composition of 3,6
mixtures.
+ + + 2+ 2+
IV Flame photometry: Estimation of Na , K , Li , Ca and Mg . Composition of the mixtures. 4,6
V Karl-Fischer titrator: Estimation of water contents in pharmaceuticals, oils, fats and paints. 4,6
VI Computers in Chemistry: Writing, compiling, and executing a computer program in C++, 5,6
for any four chemical problems given: Determination of molecular weight of an organic
compound, Determination of decay constant, half life and average life of a radioactive
element, Calculating the normality/molarity/ molality of a given solution, Calculating the
pH of a solution.
OR
Calculate the equilibrium geometry, geometrical parameters and energy of molecules:
water, methane, ethane, acetone, and acetaldehyde using MOPAC semi empirical
program.
References:
 Kanetkar Y. P., “Let us C++” 2nd Edition, BPB Publications, Delhi, 2003.
 VogelA.I., “A Text Book of Quantitative Inorganic Analysis”, Longman.
 WillardH. H., Merritt L. L. and DeanJ. A., “Instrumental Methods of Analysis”, Affiliated
East -West.
 Daniels,F. and Mathews,J. H. "Experimental Physical Chemistry", McGraw Hill, 1970.
 YadavJ. B., “Advanced Practical Chemistry”, Krishna Prakashan Media, 2015.

61
1. Semester 3
2. Course Title ELECTRONIC STRUCTURE THEORY AND APPLICATIONS
3. Course Code CHE-DE-537
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1.Understand and apply the theories of molecular mechanics and 2-Un;3- CK,PK II,III
dynamics Ap
2. Distinguish and apply various MO treatments for polyatomic 3-Ap; PK,MK II, III
molecules 4-An
3. Classify various basis sets and justify its use for a specific problem 3-Ap; CK,PK II, III, VI
4-An;
5-Ev
4. Understand the post HF methods 2-Un CK,PK II,III
5. Explain the basic theories and classification of density functional 2-Un;3-FK,CK II, III
theory Ap
6. Construct the structure of polyatomic molecule in terms of internal 6-Cr CK,PK III, VI
coordinates
7. Understand the theories of computing properties of structure and 2-Un CK,PK II, III
charge
MODULE COURSE CONTENT CO No.
No
I Molecular dynamics: Brief description of computational methods: abinitio, semi empirical, 1
and empirical methods. Molecular mechanics. Potential energy functions. Force fields.
Geometry minimization, Molecular dynamics. Periodic boundary conditions, Propagation
of Newton’s equation using Verlet, Velocity verlet and Leap-Frog algorithm.
II Ab initio Methods: Approximations. HartreeFock method. Self consistent field. Slater 2
determinants. Roothan approximation. Restricted HartreeFock (RHF), Restricted open HF
(ROHF), and Unrestricted HF (UHF) methods. Semi empirical treatments: Extended Hückel
theory. Introduction to CNDO, INDO, NDDO. Applications. Computing the matrix elements.
Slater’s rules for matrix elements. Convergence. Optimization.
III Basis sets andBasis functions. Slater type orbital (STO) and Gaussian type orbital (GTO). 3
Contracted and primitive. Basis sets. Minimal, multiple zeta, split-valence, polarized and
diffused. Pople style basis sets, designation of basis set size –Dunnings correlation
consistent basis sets Relativistic effects - Effective core potential, ECP.
IV Post HF methods-Exchange and Correlation energy. Static and dynamic electron 4
correlation, Avoided crossings and configuration mixing. Configuration Interaction (CI).
Couple cluster, Multi-Configuration and Complete active space SCF (MCSCF, and CASSCF),
Moller-Plesset Perturbation methods (MPn). Pros and Cons of these methods.
V Density Functional Theory: Development of density function theory (DFT). Density 5
matrices. Thomas-Fermi model. Hohenberg-Kohn existence and variational theorems.
Chemical potential. Kohn-Sham self consistent field method. Exchange correlation
functionals. Local density approximation (LDA), density Gradient corrections (GGA).
Hybrid and meta–GGA functionals. Advantages and applications of DFT.
VI Specifying the molecule in Cartesian and internal coordinates: Writing the Z-matrix of H2O, 6,7
CH4, ethane, Cyclopentadiene, and benzene with suitable point group. Dummy atoms and
Ghost atoms. Influence of point group in computations. Illustration by taking H 2O, and
NH3. Computing the quantities- structure, potential energy surface, and chemical
properties such as Mulliken and natural charges. Dipole moments.SCF orbital energies.

62
Koopmann’s theorem and Brillouin theorem.
References:

nd
Cramer, C. J., “Essentials of Computational Chemistry- Theories and Models”, 2 Edition, Wiley, 2004.
 Foresman, J. and Frisch, A.,“ Exploring chemistry with electronic structure methods”, GuassianInc, 2000.

rd
Jensen, F., “Introduction to Computational Chemistry”, 3 Edition, Wiley, 2017.
 Leach, A. R., “Molecular Modeling – Principles and Applications”, Addison Wesley Longman, 2001

th
Levine, I. N., "Quantum Chemistry", 7 Edition, Pearson Education Inc., 2014.

nd
McQuarrie, D. A., "Quantum Chemistry", 2 Edition,University Science Books, 2008.
 Young, D., “Computational Chemistry – A Practical Guide”, Wiley, 2001.

Model Question Paper

FOURTH SEMESTER M.Sc. DEGREE EXAMINATION, MONTHYEAR


Branch: CHEMISTRY
CHE-DE-537 ELECTRONIC STRUCTURE THEORY AND APPLICATIONS
Times: 3 Hours Max. Marks: 60

SECTION- A

Answer any 10 questions. Each question carries 2 marks.

1. What is a stochastic process? Which simulation method is most suitable for this process?
2. Which method among these is computationally least expensive for a particular problem and why?
i) molecular mechanics, ii) Semi-empirical methods and iii) ab initio methods.
3. State Koopmanns theorem. Is it applicable to open shell systems in ROHF calculations?
4. What is the major difference between single point energy calculation and geometry optimization?
5. Calculate the number of contracted and primitive basis functions for carbon if you are using 6-311+G(d,p).
6. What are the advantages of adding polarization and diffusion functions in a basis set?
7. What is correlation energy? Differentiate between Coulomb correlation and Fermi correlation.
8. Write down the form of exchange integral and its effect on total electronic energy.
9. Why density functional theory is named so instead of density function theory?
10. Differentiate between LDA and GGA.
11. What type of computation will be performed to verify if the molecule is indeed a minimum on the potential
energy surface.
12. Differentiate dummy and ghost atoms.
SECTION- B
Answer any 6 questions. Each question carries 4 marks.

13. What is boundary condition and why these are necessary for dynamic simulation?Give an account of Monte
Carlo simulations
14. Briefly explain semi empirical method giving emphasis to CNDO.
15. Explain the concept of PES? How will you identify the global minima?
16. Explain correlation consistent basis sets and the advantage of using this in computations.
17. Give an account of configuration interaction
18. Compare and contrast DFT and HF methods.
19. Write a note on the influence of point groups in calculations?
20. What is meant by geometry optimization? Explain the steps.

63
SECTION- C
Answer any two questions. Each question carries 8 marks
21. a) Explain ‘Force Fields’
b) What are Pople style basis sets? Briefly explain the classification and its relevance. (4+4)

22. Explain and differentiate with examples the various approximations employed under density functional
theory methods.
23. Explain in detail the various steps involved in HF methods. Also, differentiate RHF and UHF methods.
24. Explain Kohn-Sham theorem and applications

64
1. Semester 3
2. Course Title PHOTOPHYSICAL PROCESSES AND APPLICATIONS
3. Course Code CHE-DE-538
4. Credits 3
5. CO TL KL PSO No.
On completion of the course, students should be able to:
1. Summarize and differentiate various photophysical processes in 1-R; 2- FK, 01, 02
molecular systems U; 4-An CK

2. Exemplifies and distinguish diverse absorption and emission 4-An; 5- FK, 01, 02
phenomenon observed in molecular systems E CK
3. Explain the concepts and demonstrate the applications associated 2-U; 3- CK 01, 02
with photoinduced electron transfer and energy transfer Ap
4. Illustrate the techniques and instrumentation of fluorescence and 2-U; 3- FK, 01, 02
other fast light induced processes / reactions Ap CK
5. Identify and design molecular sensors for metal ions, anions and 4-An; 6- CK, 02, 03
neutral molecules based on various photo-chemical/-physical Cr MK
processes
6. Describe and compare the properties and applications of light 2-U; 3- FK, 01, 02
active semiconductor nanoparticles and lanthanide based systems Ap; 5-E CK
7. Comprehend the properties and applications of metal-ligand 2-U; 4- CK, 01, 02
complexes and AIE luminogens An MK
8. Appreciate the processes happening in natural photosyntheitic 2-Un; 4- FK, 01, 02
systems An CK
9. Elaborate reactions happening in artificial solar energy converting 4-An; 5- CK, 01, 02,
systems and compare it to those in natural photosynthetic systems E MK 03
MODULE COURSE CONTENT CO No.
No
I Photophysical Properties of the Electronically Excited Molecules:Basic principles of 1, 2
photochemistry: Absorption of radiation-Beer Lambert's law. Electronic transitions.
Frank Condon principle. Jablonski diagrams. Nonradiative transitions. Internal
conversion and inter system crossing. Radiative transitions: Fluorescence emission,
triplet states and phosphorescence. Absorption complexes. Charge transfer absorption.
Excimers. Exciplexes. Delayed fluorescence. Chemiluminescence.
II Bimolecular Processes: Fluorescence quenching. Collisional quenching. Stern-Volmer 3
equation. Static quenching Photoinduced electron transfer (PET): Concepts and
theories, electron donors and acceptors, quantum yield, efficiencies and lifetimes,
intermolecular, intramolecular and supramolecular PET. Fluorescence resonance
energy transfer (FRET): Trivial or radiative mechanism; Forster and Dexter type energy
transfer. Energy transfer versus electron transfer. Applications of electron transfer and
energy transfer.
III Techniques and Instrumentation:Light sources, filters and monochromators: 4
Incandescent lamps and arc lamps, optical filters, spectrographs and monochromators.
Lasers as excitation sources: General principles, Two, three and four level lasers, Solid
state lasers (Ruby and Nd/YAG) and gas lasers. Luminescence measurements: Steady-
state fluorescence spectroscopy. Luminescence quantum yield measurements, Time-
resolved fluorescence spectroscopy, single photon counting, Detection and kinetics of
reactive intermediates, Transient absorption spectroscopy: Nanosecond laser flash
photolysis and Picosecond laser flash photolysis.

65
IV Application of fluorescence in chemical sensing: Various approaches of fluorescence 5
sensing, Fluorescent pH indicators, Fluorescent molecular sensors based on ion or
molecular recognition: Recognition units and topology, recognition based on
photoinduced electron transfer(PET), photoinduced charge transfer (PCT), Excimer
formation and disappearance and Forster resonance energy transfer (FRET).
Fluorescent sensors for Metal ions (based on all above mentioned recognition
mechanisms), Fluorescent sensors for anions and neutral molecules.
V Novel Fluorophores:Semiconductor Nanoparticles: Spectral properties of quantum 6,7
dots, Labeling cells with quantum dots, Quatum dots and Resonance Energy Transfer
(RET), Lanthanides: RET with lanthanides, Lanthanide nanoparticles, Near-infrared
emitting lanthanides, Long-lifetime metal–ligand complexes: Introduction to metal–
ligand probes, Spectral properties of MLC probes, Metal-ligand complex sensors,
Aggregation induced emissive (AIE) fluorophores: Mechanism of AIE and applications.
VI Solar Energy Conversion:Natural photosynthetic system: Light dependant reactions, 8,9
photosynthetic reaction centre, Z-scheme of photosynthesis. Artificial photosynthesis,
conversion of solar energy to chemical and other forms of energies. Solar water
splitting. Photocatalytic hydrogen production, Photocatalytic carbon dioxide reduction.
Photovoltaic cells: Polymer solar cells and dye sensitized solar cells. Photo-biochemical
energy production.
REFERENCES
 Lakowicz, J. R. “Principles of Fluorescence Spectroscopy”, 3 Ed., Springer, New York, 2006.
rd

 Valeur, B B. “Molecular Fluorescence: Principles and Applications”, Wiley-VCH Verlag


 Kavarnos,G. J. “Fundamentals of Photoinduced Electron Transfer”, VCH publishers
 Rohatgi-Mukherjee, K. K. “Fundamental of Photochemistry”, New Age International (P) Ltd.,New Delhi, 1986.
 Turro, N. Ramamurthy,J. V. Scaiano, J. C. “Principles of Molecular Photochemistry”, University Science,
Books, CA, 2009.
 Gratzel, M. “Energy Resources through photochemistry and catalysis, Academic Press, 1983.Inc., New York,
1993.

ADDITIONAL REFERENCES
 Barber J, Tran PD. “From natural to artificial photosynthesis”, J R Soc Interface 10:20120984.
http://dx.doi.org/10.1098/rsif.2012.0984, 2013
 Depuy C. H. and Chapman,O. L. “Molecular Reactions and Photochemistry”,
 Feng,G. Kwok, R. T. K. Tang, B. Z. and Liu,B. “Functionality and versatility of aggregation-Induced Emission
Luminogens”, Appl. Phys. Rev., 4, 021307 (2017)GmbH, Weinheim, 2002.
 Mei, J. Leung, N. L. C.Kwok, R. T. K. Lam, J. W. Y. and Tang, B. Z. “Aggregation-Induced Emission: Together
We shine, United We Soar” Chem Rev., 115, 11718-11940 (2015). Prentice Hall of India Pvt. Ltd., 1988.
 Serpone N. and Pelizzetti, E. “Photocatalysis,” Wiley, New York, 1989.
 Suppan, P. “ Chemistry and light”, Royal Society of Chemistry, Cambridge, 1994.

66
Model Question Paper

THIRD SEMESTER M.Sc. DEGREE EXAMINATION Month Year


Branch: CHEMISTRY
CHE-DE-538: PHOTOPHYSICAL PROCESSES AND APPLICATIONS

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. State and Explain Frank Condon principle.


2. Guanosine has a maximum absorbance of 275 nm. 275 = 8400 M-1 cm-1 and the path
length is 1 cm. Using a spectrophotometer, you find that the absorbance at 275 nm is
0.70. What is the concentration of guanosine?
3. What is Stern-Volmer equation? How it is useful in distinguishing static and dynamic
quenching?
4. Explain the concept of donor and acceptor in photoinduced electron transfer (PET) with
suitable examples.
5. Which are the light sources used in the UV-Vis absorption spectrophotomerter?
6. Experimentally how can you characterise the triplet state of an organic chromophore?
7. What is a fluorescent pH indicator? Explain with an example.
8. Exemplify the concept of excimer based fluorescence sensor.
9. Luminescence lifetimes of metal-ligand complexes are usually high compared to that of
pure organic fluorophores. Why?
10. How luminescence originates in quatum dots?
11. What is the function of redox couple in dye sensitized solar cell?
12. Write a note on photocatalytic carbon dioxide reduction.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Exemplify the concept of delayed fluorescence.


14. Briefly discuss about the phenomenon of chemiluminescence with suitable examples.
15. What is Fluorescence resonance energy transfer (FRET)? Briefly explain the Foster type
energy transfer.
16. Briefly explain the principle of working of lasers.
17. Portrait the working of metal ion sensors based on any two different recognition
mechanisms.
18. Briefly represent the mechanism of aggregation induced emission.
19. Quantum dots are useful candidates in bio-medical field. Justify the statement.

67
20. Briefly discuss about dye sensitised solar cells.

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Write note on Photoinduced electron transfer (PET) in molecular systems. How can we
make use of PET in designing molecular sensors?
22. i) Illustrate and explain various radiative and non-radiative transitions in molecular
systems with the help of Jablonski diagram.
ii) Explain the principle and instrumentation of Transient absorption spectroscopy.
(4 + 4)

23. Discuss the photochemistry of metal-ligand complexes. Exemplify their use in solar
water splitting.

24. i) Illustrate the instrumentation of steady-state fluorescence spectroscopy.

ii) Illustrate the light-dependent reactions in natural photosynthesis.


(4 + 4)

68
1. Semester 3
2. Course Title NEW METHODS IN ORGANIC SYNTHESIS
3. Course Code CHE-DE-539
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Use retrosynthetic method for the logical dissection of complex 3- CK II, III,
organic molecules and devise synthetic methods Ap, VI
4-
An,
6-
C
2. Use various reagents and organic reactions in organic synthesis 3- FK, CK III, VI
Ap
3. Gain expertise in asymmetric synthesis and catalysis 3- FK, CK VI
Ap
MODULE COURSE CONTENT CO No.
No
I The Disconnection Approach - Designing a synthesis, FGI, 1
Synthons, order of events, choosing a disconnection, synthesis of
aromatic compounds, chemoselectivity in synthesis – one group C-X
disconnections – alcohols, ethers, sulphides, alkyl halides, two group
C-X disconnections, 1,1- and 1,2- C-C disconnections, one group C-
C disconnections, enolate chemistry, two-group disconnections, 1,1-,
1,2-, 1,3-, 1,4- and 1,5- difunctionalized compounds.
II Retrosynthesis in Action - Advanced strategies, retrosynthesis in 1
industry, stereoselectivity and regioselectivity in synthesis, using
alkenes, alkynes and nitro compounds in synthesis, reconnections,
retrosynthetic analysis and synthesis – practice problems

III Heterocyclic Ring Synthesis - Three, four, five and six membered 2
ring synthesis and retrosynthesis, aromatic heterocycles, aromatic
heterocycles with two heteroatoms, rearrangements in synthesis,
electrophilic substitution reactions, named reactions in heterocyclic
synthesis.
IV Modern Organic Synthesis - Nef reaction, Kulinkovich reaction, 2
Ritter reaction, Seyferth-Gilbert homologation, Tishchenko reaction,
Fritsch-Buttenberg-Wiechell rearrangement, Corey-Fuchs reaction,
Noyori reaction. Brook rearrangement. Tebbeolefination. Metal
mediated C-C and C-X coupling reactions: Heck, Stille, Suzuki,
Suzuki-Miyaura, Negishi-Sonogashira, Nozaki-Hiyama, Buchwald-
Hartwig, Ullmann and Glaser coupling reactions. Wohl-Ziegler
reaction. Introduction to MCR, Ugi and Passerini reactions, Click
reactions, olefin metathesis.
V Asymmetric Synthesis - Organocatalysis, Prolines and NHCs – 3
synthesis and reactivity, Transition metal mediated reactions in
organic synthesis, Olefin metathesis, Grubbs catalysts, Enantiomers
and diastereomers. resolution methods, Stereospecific and
stereoselective synthesis, Asymmetric Synthesis - Principles,
General strategies, Chiral Pool strategy, Chiral Auxiliaries,

69
Asymmetric Diels Alder Reaction, Chiral Reagents – Binol
Derivatives of LiAlH4, Chiral Catalysts – CBS Catalyst.
VI Reagents – Use of DDQ, iodobenzenediacetate, CAN, manganese 2
acetate, FeCl3, NMO, Dess Martin periodinane, SmI2, N-
heterocyclic carbenes, Na tetracarbonyl ferrate, benzenetricarbonyl
chromium: TEMED, TEMPO, TMS, CBr4 + Ph3P

REFERENCES
 Warren,S. “Organic Synthesis – The Disconnection Approach”, John Wiley and Sons, 2004
 P. S. Kalsi “Organic Synthesis through Disconnection Approach” MEDTEC, 2014
 Gilchrist, T. L. “Heterocyclic Chemistry.” Pearson, Third Edn., 2005.
 Norman, R. O. C. “Principles of Organic Synthesis”, Chapman and Hall, 2nd Edition, 1995.
 Clayden, J., Geeves, N and Warren, S. “Organic Chemistry”, OUP.

ADDITIONAL REFERENCES
 Joule J. A and Mills K. “Heterocyclic Chemistry”, 4th Edition, UK, Blackwell Science, 2000.
 Taber, D “Organic Synthesis – State of the Art 2003-2005”.

Model Question Paper


THIRD SEMESTER M.Sc. DEGREE EXAMINATION 2020
Branch: CHEMISTRY
CHE-DE-539NEW METHODS IN ORGANIC SYNTHESIS
Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Suggest synthetic equivalents for a) PhCH2- and b) PhCH2+


2. 1-Butyne can be converted to butanal by using hydroboration oxidation. Illustrate.
3. Reaction of 4-hydroxy aniline with acetyl chloride is used for the synthesis of an
analgesic. Identify the compound and depict the synthetic scheme.
4. How is m-nitro toluene synthesized from toluene?
5. Complete the following reaction sequence.
O COCH3
HO
S S
HgCl2
?
?
H2O
S Li
S

6. How is thiophene converted to thiophene-2-carbaldehyde?


7. How are azetidines and azetidine-2-ones synthesized?
8. Suggest a method to convert benzophenone to diphenyl acetylene and illustrate the
mechanism.
9. Predict the product
O

Pd(OAc)2
NC Br + H N
2 Ph ?
XantPhos, Cs2CO3

10. Give an example each for Grubbs 1st and 2nd generation catalysts.

70
11. How are BINOL derivatives of LiAlH4 synthesized? Give one application.
12. What is the product formed when benzene tricarbonyl chromium complex is treated with
BuLi followed by TMSCl? Illustrate.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Retrosynthesis of a 1,4-diketone is shown below. Complete it and suggest the synthesis.
O O
N
Na+
O NO2 NO2
+

O O O
O
14. The retrosynthetic analysis of Propranolol, a drug used for heart ailments, is shown
below. Suggest a synthetic route.

O N O OH
H Cl
O
OH
+

15. Explain Hantzsch pyridine synthesis.


16. How are the following conversions done?
O Br
? O
i)
O O

O O

?
ii) Ph Cl Ph

Ph

17. Give an example each for ROM and RCM.


18. Explain this reaction
O H
N

O
N H
Bn H 20 mol% O
+

O
OMe

OMe endo/exo > 200:1


19. Depict one application of CBr4 + Ph3P reagent.
PCy3 Ph
Cl
Ru
CO2Me Cl
PCy3

CO2Me
?
20. Predict the product.

71
SECTION-C
Answer any 2 questions. Each question carries 8 marks
21 What reagents can bring about the following conversions
Br a b

c O

22. Suggest a retrosynthesis for OH


23. i) Describe the reactivity of SmI2, CAN and Mn(OAc)3 providing examples. (3x3)
ii) What is DDQ? What is it used for?
iii) Explain the structure and importance of TEMPO
24. Depict the schemes with reagents and illustrate the mechanisms of Perkin, Stobbe,
Dieckmann and Knoevenagel reactions.

72
1. Semester 3
2. Course Title Introduction to Chemical Biology and Anti-Cancer Research
3. Course Code CHE-DE-540
4. Credits 3
5. CO: On completion of the course, students should be able to: TL KL PSO
No.
1. Describe the basic structural difference between prokaryotic 1-R, 2-Un FK PSO2
and eukaryotic cells
2. Describe the structure and chemical composition of nucleic acids, 2-Un, 3-Ap FK PSO2
protein, carbohydrates and lipids.
3. Describe and evaluate the chemical aspects of biological process 2-Un, 3-AP FK, PSO2,
and cell anatomy 5-E CK PSO3
4. Describe in interlink between the nucleic acid sequence and 2-Un, 3-Ap FK, PSO2,
protein synthesis to control various functions in cells CK PSO3
5. Correlate the evolutionary history with cellular and molecular 2-Un, 3-Ap, FK, PSO2
biology 5-E CK PSO3
6. Explain and correlate the genetic information with cancer growth 2-Un, 4-An, FK, PSO2
and new therapeutic techniques in anti- cancer researchworking 5-E CK PSO3
protocols. PK
7. Describe about some fundamental aspects biochemical assays 2-Un, 3-Ap FK,PK PSO2
PSO4
MOD COURSE CONTENT CO No.
I The beginning of life, the cell: Cells, the structural and functional units of all living CO1
organisms; Three distinct domains of life; Eukaryotic and prokaryotic cell CO3
structure; Structural hierarchy in the molecular organization of cells; Cell Cycle and CO5
Cell-Growth Control; Macromolecules in cell constitution; Stereospecific
interaction between biomolecules; Basics of energy production in cell; Genetic
foundations in cell; Prebiotic chemistry and biological evolution; Molecular
anatomy and evolutionary relationships.
II Nucleic acids: structure and biological relevance:Deoxyribose nucleoside and CO2
nucleotide; Phosphodiester and glycosidic bond; Double helix structure of DNA; CO4
DNA super coiling; DNA topologies; Significance of DNA G-quadruplex; DNA-
replication, repair and recombination; Reversible denaturation and annealing
(renaturation) of DNA; DNA stability and damage; Chemical synthesis of DNA;
Amplification of a DNA segment by the polymerase chain reaction (PCR).DNA
sequencing by the Sanger method; Nucleotides as a carrier of chemical energy in
cells; Adenine nucleotides as a components of enzyme cofactors; Gene and
chromosomes; Ribose nucleic acid (RNA); secondary structures of RNA; Different
types of RNAs and their biological role in cell; DNA-Dependent Synthesis of RNA;
RNA Processing; Transcription and translation; RNA-Dependent Synthesis of RNA
and DNA.
III Proteins, carbohydrates and lipids: Amino acids; classifications of amino acids; CO2
acid-base properties of amino acids; peptides and polypeptides; structure of CO4
protein; Chemical synthesis of peptides; Ramachandran plot; secondary structure
of protein; Protein tertiary and quaternary structures; Structural diversity and
functional diversity in globular proteins; Stable folding patterns in proteins;
Protein denaturation and folding; Enzymes and the working principle; Primary
structure of carbohydrate; monosaccharides and disaccharides; Fischer projection
and Haworth perspective formulas; Polysaccharides; Structural and functional
roles of polysaccharides; Lipids;Sphingolipids; Storage lipids; Polyunsaturated fatty
acids; Structural lipids in membrane; Lipids as signals, cofactors, and Pigments

73
IV Membrane transport, biosignaling, bioenergetics and metabolism:The CO4
composition and architecture of membranes;membrane proteins; Transbilayer
movement of lipids; Receptor-mediated endocytosis, caveoline mediated
transport; Solute transport across membrane; Glucose transport; Ion transport;
ATP driven transport; Ion channels; General features of signal transduction; G
protein–coupled receptors and second messengers; GPCRs in vision, olfaction, and
gustation; Receptor Tyrosine Kinases; Biochemical reactions in biological energy
transduction; Free energy change associated with ATP, acetyl-coenzyme A, and
phosphoenolpyruvate (PEP); ATP as the energy source for cell functions; Biological
Oxidation-Reduction Reactions; Types of coenzymes and proteins serve as
electron carriers; Glycolysis-the two phase of glycolysis; Feeder pathways for
glycolysis; Fates of pyruvate under anaerobic conditions: Fermentation;
Gluconeogenesis.
V Strategies in cancer therapeutics and imaging:Oncogenes, Tumor suppressor CO6
genes, and programmed cell death-apoptosis; Cancer metabolism; Multidrug
resistance; Personalized medicine; Cancer therapeutic and imaging techniques-
Metal complexes as anti-cancer drugs; photodynamic therapy (PDT), Photothermal
therapy (PTT), Immunotherapy and gene therapy; Positron Emission tomography
(PET), ImmunoPET, Magnetic resonance imaging (MRI) in cancer imaging;
Nanomaterial for therapy and theranostics; Protein inhibition; heat shock protein
(HSP) inhibition; Synergistic cancer therapy; Mitochondria targeting therapies.
VI Biochemical tools and working protocols:Cell culture protocol; Cell proliferation CO7
assays; Fluorescence and confocal microscopy; Fluorescence life time imaging
(FLIM); DNA cloning and recombinant DNA technology; Bacterial and yeast
artificial chromosomes; reverse transcriptase PCR (RT-PCR); quantitative PCR (q-
PCR); Polypeptide sequencing; Purification, Detection, and Characterization of
Proteins; Ion exchange chromatography; SDS Gel electrophoresis; Investigating
proteins with mass spectrometry; Fusion proteins and immunofluorescence
proteins for localization of proteins in cells; Protein-protein interaction studies;
Tandem affinity purification (TAP) tags; DNA microarrays to investigate RNA
expression patterns and other Information; CRISPR/Cas systems; Human genome
sequencing-applications.
References:
 Lehinger Principles of Biochemistry, D. L. Nelson and M. M. Cox, W H Freeman, New York, Mac millan
th
learning,7 edition, 2017.
 Molecular cell biology, H. Lodish, A.Berk, P. Matsudaira, C. A. Kaiser, M. Krieger, M. P. Scott, L. Zipursky and J. Darnell.
th
W.H.Freeman & Co Ltd, 5 edition, 2007.
 Chemical Biology: A practical course, H. Waldmann and P. Janning. Wiley -VCH Verlag GmbH & Co. 2004.
 Foundations of Chemical biology, C.M. Dobson, J.A. Gerrard and A.J. Pratt. Oxford Univ. Press. 2002.
 Biochemistry, J. M. Berg, J. L. Tymoczko and L. Stryer. W. H. Freeman and Company, New York References.
 Chemical Biology: from small molecules to systems biology and drug design, S. L. Schreiber, T. Kapoor and G. Wess.
Wiley – VCH Verlag GmbH & Co. Vol-1, 2007.
 Chemical Biology: Application and Techniques, B.Larijani, C. A. Rosser and R.Woscholski, John Wiley & Sons Ltd. England,
2006.
 Essentials of Chemical Biology; Structure and Dynamics of Biological Macromolecules, A. Miller, J. Tanner, John Wiley &
Sons Ltd, 2008.
Additional References
 Nanotechnology for Multimodal Synergistic Cancer Therapy, W. Fan, B. Yung, P. Huang, and X. Chen, Chem. Rev. 2017,
117, 13566-13638.
 Imaging and Photodynamic Therapy: Mechanisms, Monitoringand Optimization, J. P. Celli, B. Q. Spring, I.Rizvi, C. L.
Evans, K. S.Samkoe, S.Verma, B. W. Pogueand T.Hasan, Chem. Rev. 2010, 110, 2795-2838.

74
 Functional Nanomaterials for Phototherapies of Cancer, L. Cheng, C. Wang, L. Feng, K. Yang and Z. Liu, Chem. Rev. 2014,
114, 10869−10939.
 Metal Drugs and the Anticancer Immune Response, B.Englinger, C.Pirker,P.Heffeter, A.Terenzi,C. R. Kowol, B. K. Keppler
and W. Berger, Chem. Rev. 2019, 119, 1519−1624

Model Question Paper

THIRD SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-DE-540: Introduction to Chemical Biology and Anti-Cancer Research

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Mention four points to differentiate eukaryotic and prokaryotic cells.


2. Silicon is in the same group of the periodic table as carbon and, like carbon, can form up to four
single bonds. In that case, what is the possibility of replacing silicon with carbon in
biomolecules? Justify your answer.
3. What is prosthetic group in a protein? Explain with example.
4. How a phosphodiester linkage is formed in a DNA and how it is important in determining the
structural features?
5. Compare the stability of DNA and RNA in alkaline condition. Justify your answer.
6. Differentiate Watson-crick and Hoogsteen hydrogen bonding with example.
7. How PCR and RT-PCR differs?
8. What is recombinant DNA?
9. What is apoptosis?
10. What is a plasmid?
11. Describe the advantages of FLIM over normal fluorescence microscopy.
12. Write a short note on DNA G4 structure and its biological relevance.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Write a note on abiotic origin of biomolecules.


14. Sketch in detail the mutual dependence of DNA and protein.
15. Explain the difference between ion exchange, size exclusion and affinity chromatography for
protein purification.
16. Plot the reaction sequence in Edman degradation method of peptide sequencing.
17. If you want to make a double stranded DNA with the oligomer 5’-ACCTGGTCACATTGG-3’,
how you will execute the synthesis? Explain in detail.
18. What is the chemical background of MTT assay?
19. Sketch the conformational difference in the polysaccharides cellulose and amylose.
20. In samples of DNA isolated from two unidentified species of bacteria, X and Y, adenine makes
up32% and 17%, respectively, of the total bases. What relative proportions of adenine,

75
guanine,thymine, and cytosine would you expect to find in the two DNA samples? One of these
species was isolated from a hot spring (64 °C). Which species is most likely thethermophilic
bacterium, and why?

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Explain in detail the PCR procedure of DNA amplification. (8)

22. (i) What is HSP90 and how HSP90 inhibitors can act as an anti-cancer drug? (4)
(ii)What are the major components in PDT and how the therapeutic effect is generated? (4)

23. (i) Explain Ramachandran plot and how this helps to test the quality of a predicted 3D structure
of a protein. (5)
(ii) Explain the effect of pH on the conformation of α-helical secondary structures of poly(Glu)
and poly(Lys). (3)
24. Explain the role of G protein–coupled receptors (GPCRs) in vision, olfaction, and gustation. (8)

76
FOURTH SEMESTER

1. Semester 4
2. Course Title COMPREHENSIVE VIVA
3. Course Code CHE-CC-541
4. Credits 2
5. CO TL KL PSO No.
With this, the student should be able to
1. Do a comprehensive revision of the topics studied so far in the 4-An,5- CK III, VII,
programme E VIII
2. Get trained to attend an interview-mode examination 4-An, MK III,
5-E VII,VIII
COURSE CONTENT CO No.
Comprehensive viva will include various topics of the core courses studied in the first three semesters

77
1. Semester 4
2. Course Title DISSERTATION
3. Course Code CHE-CC- 542
4. Credits 14
5. CO TL KL PSO No.
On completion of the course, students should be
able to:
1. Conduct a literature survey 3-Ap, 5-E PK VI, VII,VIII
2. Design and execute small reaction schemes 5-E, 6-C PK, MK VI,VII,VIII
3. Independently write scientific reports 6-C CK,PK VII, VIII
4. Communicate through various forms of 3-Ap CK VIII
presentation

78
1. Semester 4
2. Course Title APPLIED CHEMISTRY
3. Course Code CHE-DE-543
4. Credits 3
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Understand various chemical industry processes 1-R, FK, CK I, II
2-Un,
2. To appreciate the role of chemistry in day-to-day human life 2-Un, FK, CK I, II, III
3-Ap
4-An
3. To apply chemistry principles in industry and chemical engineering 3-Ap, CK, PK I, III
5-E
MODULE COURSE CONTENT CO No.
No
I Petroleum, Fuels &Combustion, Lubricants - Petroleum:Petroleum, 1, 3
cracking, Synthetic petrol, Refining of gasoline, Reforming, Chemical
structure of fuel and knocking. Octane Rating of fuels, Cetane Rating, Diesel
engine fuel, Kerosene, LPG as a fuel.
Fuels &Combustion:Classification, Calorific value, Types, Determination by
Bomb calorimeter, Dulong's Formula, Analysis of Coal, Proximate and
Ultimate analysis, Fuel gas analysis, Significance, Numericals,
Carbonization of Coal, Manufacture of metallurgical coke by Otto
Hoffman's by product oven, Combustion calculations.
Lubricants:Functions of lubricant, Mechanism of lubrication, Fluid or
Hydrodynamic Lubrication, Thin film or Boundary lubrication & Extreme
pressure lubrication. Lubricants for Extreme ambient conditions and for
special applications. Properties of lubricants and tests.
II Corrosion and Protective Coatings - Corrosion and its Control:Nernst 1, 2, 3
Theory, Standard Electrode Potential, Galvanic Series, Concentration cell,
Types of corrosion: Uniform and Galvanic, Erosion, Crevice, Pitting,
Exfoliation and Selective leaching, Inter-angular Stress, Waterline, Soil,
Microbiological. Theories of corrosion: Acid, Direct Chemical attack,
Electrochemical, Corrosion reactions, Factors affecting corrosion, Protective
measures against corrosion, Sacrificial anode, and impressed current cathode
protection.
Protective Coatings:Paints: Constituents, functions & mechanism of drying.
Varnishes and Lacquers; surface preparation for metallic coatings,
electroplating (gold) and electroless plating (Nickel), anodizing, phosphate
coating, powder coating & antifouling coating.
III Applied Inorganic Chemistry - Introduction to chemical industry: Flow sheet 1,3
preparation. Principles of process selection and operation selection. Basic
raw materials and routes to major inorganic products. Flow sheets and
engineering aspects of the manufacture of sulfuric acid, ammonia, urea,
glass.Refractories:Definition, Classification with examples; Criteria of a
good refractory material; Causes for 79 the failure of a Refractory Material.
Flow sheet and engineering aspect of the manufacture of Refractories.
IV Portland Cement:Manufacture of cement, Dry and Wet process, Flow sheet 1, 3
and engineering aspect of the manufacture of Portland cement, Important
process parameters for manufacturing a good cement clinker. Characteristics
of the constitutional compounds of cement.Additives for cement, Properties,
General composition, testing of cement, Chemical & physical requirement.
V Applied Organic Chemistry - Raw materials and routes to major organic 1,3
products. Flow sheets and engineering aspects of the manufacture of
important products such as nitrobenzene, vinyl chloride, soaps, detergents
and hydrogenation of oils.
Pharmaceuticals: manufacturing process of aspirin, vitamin A and
paracetamol.
Pesticides: manufacture of BHC, DDT, Carbaryl and Malathion.
Manufacture of dyes.
Cosmetics: Talcum Powder, Tooth pastes, Shampoos, Nail Polish, Perfumes,
soaps, and detergents - General formulations and preparation - possible
hazards of cosmetics use.
Adulterants: Adulterants in milk, ghee, oil, coffee powder, tea, asafoetida,
chilli powder, pulses and turmeric powder - identification. Color chemicals
used in food-soft drinks and its health hazards.
VI Polymer Chemistry - Polymers: Types of Polymerization. Thermoplastics & 1,2,3
thermosetting polymers. Preparation, properties and applications of the
Polyethylene, Teflon, PVC, Nylon, Phenol formaldehyde & Urea
Formaldehyde. Silicone resins, silicone fluids, silicone greases.
Polyurethanes, foamed or cellular plastics.Elastomers: Natural rubber,
Vulcanization of rubber & Synthetic rubber.

REFERENCES

 Baird, C “Environmental Chemistry”, Publisher WH Freeman, 2008


 Kulkarni, V & Ramachandran,T V” Environmental Management”, Teri Press, New Delhi, 2009.
 Kumar, R & Singh,R N “Muncipal water and waste water treatment”, Teri Press, 2008
 Patwardhan,I A.D “industrial Solid Wastes”, Teri Press, New Delhi, 2012
 Varashney, C.K. “Water pollution and management”, Wiley Eastern Ltd., Chennai - 20.

ADDITIONAL REFERENCES

 Bagavathi Sundari K., “Applied chemistry”, MJP Publishers.


 Charles E.Dridens, “Outline of Chemical Technology”, East-West Press Publishing, 1973.
 De, A .K. “Environmental Chemistry”
 Ghosh, Jayashree “Fundamental concepts of applied chemistry”, S.Chand & Co Ltd., New Delhi.
 Meyer, L. Hoagland “Food chemistry”, CBS publishes & distributors, 2004.
 Poucher, W.A. “Perfumes, Cosmetics and soaps”, Vol 3, Springer, 2000.
 Sharma, B. K. “Industrial Chemistry”, Goel publishing house, Meerut.
 Shreve R. Norris & Joseph A.Brink.Jr, “Chemical process industries”, McGraw Hill, 1984.
 Srilakshmi, B. “Food Science”, III Edition, New age international publishers, 2005.
 Wiseman,P. “Industrial Organic Chemistry”, Elsevier Science Ltd, 1972.
************

80
Model Question Paper
FOURTH SEMESTER M.Sc. DEGREE EXAMINATION 2020
Branch: CHEMISTRY
CHE-DE-543: APPLIED CHEMISTRY

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Differentiate between octane number and cetane number.


2. A furnace is heated by combusting a gaseous fuel of composition 29% CO, 9% CO2, 16% H2 and
46% N2 with dry air. The Orsat analysis of products of combustion (POC) is 15% CO2, 7% O2
and 78% N2. Calculate the volume of products of combustion (POC) at STP and at 1000 deg C.
3. What are the various types of corrosion?
4. Differentiate between electroplating and electroless plating.
5. What are the criteria for a good refractory material?
6. What are the common additives added in cements?
7. Depict the flowsheet for manufacture of sulphuric acid.
8. Differentiate between soaps and detergents chemically.
9. How is BHC and DDT manufactured?
10. What are the chief adulterants in milk and how are they determined?
11. How is Teflon manufactured? What are its applications?
12. Discuss monomers for polyurethane synthesis.
SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. Discuss the process of rubber vulcanization and its importance.


14. How is paracetamol and Vitamin A synthesized in lab?
15. Differentiate between thermoplastics and thermosetting plastics giving applications for both.
16. Discuss the dry and wet processes for cement manufacture.
17. Explain the factors causing corrosion and prevention strategies.
18. How is glass manufactured industrially? Explain using a flow chart.
19. What is meant by hydrodynamic lubrication? Give examples.
20. A natural gas analysing 85% CH4, 5% C2H6 and 10% N2 with air such that percentoxygen in POC
remains at 2% on dry basis. Assume complete combustion, calculate (a) analysis of POC (dry
basis), and (b) % excess air.
SECTION-C
Answer any 2 questions. Each question carries 8 marks
21. Depict a diagram for the bomb calorimeter. Explain its principle, working and application.
22. Estimate the redox potential of a natural water that is in equilibrium with the atmosphere
at pH 7 and 298 K. What fraction of a dilute solution Fe2+ will be in its oxidized form
Fe3+ in such a water?The relevant E°s are1.23V for O2(g) + 4H+ + 4e–→ 2H2O and0.77V
for the Fe3+/Fe2+ couple.
23. Why is hydrogenation of oil important? Explain the process, give example and
application.
24. Discuss the synthesis of nylon, phenol-formaldehyde, urea-formaldehyde and silicone resin.

81
Semester 4
Course Title ANALYTICAL AND INSTRUMENTAL METHODS
Course Code CHE-DE- 544
Credits 3
CO: On completion of the course, students should be able to: TL KL PSO No.
1. Describe and implement the fundamentals of data analysis and 2-Un, 3-Ap FK PSO1
analytical procedures involved in environmental quality control PK PSO2
PSO4
2. Describe and classify principles and theory behind various 2-Un FK PSO1
chromatographic techniques. CK PSO4
PK
3. Explain and demonstrate the theory, principle and 2-Un, 3-AP CK PSO1
instrumentation of various analytical and spectroscopic PK PSO4
instruments
4. Explain the basic principles and instrumentation of radiation 2-Un FK PSO1
analysis methods CK PSO2
PSO4
5. Explain and compare the principle, instrumentation and 2-Un, 4-An FK PSO1
application of thermal, electro and surface analysis techniques CK PSO4
PK
MOD. COURSE CONTENT CO No.
No
I Data Analysis and Procedures Involved in Environmental Analysis: Accuracy and CO1
precision. Evaluation of analytical data, The mean and median. Standard
deviation, variance and coefficient of variation. Classification of errors.
Minimization of errors. Significant figures and computations. Statistical methods
in analysis. Students T test, Rejection of suspected value, Q test. Analytical
procedures involved in the environmental monitoring of water quality- BOD, COD,
DO, nitrite and nitrate, iron, fluoride, soil moisture, salinity, soil colloids, cation
and anion exchange capacity. Air pollution monitoring: Control measures for air
pollutants. sampling and collection of air pollutants-SO2, NO2, NH3, O3, and SPM.
Principle of the analysis of milk and starch based food materials, Analysis of drugs,
oils and fats.
II Chromatographic Methods: Principles, instrumentation and applications of CO2
column chromatography, paper chromatography, thin layer chromatography, ion-
exchange chromatography, Gas chromatography and HPLC. Detectors,
Hyphenated techniques, Capillary Electrophoresis, Introduction to Chiral
Chromatography, Molecular Exclusion Chromatography, Affinity Chromatography.
Introduction to Method development and analysis of samples using the above
techniques.
III Introduction to Instrumental Methods: Electrical and nonelectrical data domains- CO3
transducers and sensors, detectors, examples for piezoelectric, pyroelectric,
photoelectric, pneumatic and thermal transducers. Criteria for selecting
instrumental methods precision, sensitivity, selectivity, and detection limits.
Signals and noise: sources of noise, S/N ratio, methods of enhancing S/N ratio–
hardware and software methods. Electronics: transistors, FET, MOSFET, ICs,
OPAMs. Application of OPAM in amplification and measurement of transducer
signals. 82
IV Radiation Analysis Methods: Measurement of radioactivity. Detection counters. CO3, CO4
Ionization chamber, Cloud chamber, Bubble chamber, Proportional counter,
Geiger counter, Scintillation counters, Neutron activation analysis. Isotope
dilution methods. Introduction to Positron emission Tomography, Working of
nuclear reactors.
V Thermal, Electro and Surface Analysis Methods: Principles, instrumentation and CO3, CO5
applications of thermogravimetry (TG), derivative thermogravimetry (DTG),
differential thermal analysis (DTA) and differential scanning calorimetry (DSC).
Analysis of samples using the above instruments- Principles, instrumentation and
applications of Electrogravimetry, Coulometry, Polarography, Amperometry,
Cyclic voltametry, Potentiometry and Conductometry. Analysis of samples using
the above instruments. Introduction to SEM, TEM, AFM and other surface
characterization techniques.
VI Fundamentals of Spectrochemical Methods: Spectrophotometers - Sources of CO3
Light , Lamp and lasers, Monochromators, Detectors- PMT, Photodiode array,
Charge coupled device, Infrared Detectors, Optical Sensors, Dealing with noise-
Signal Averaging, Types of Noises, Fourier transformation in infrared
Spectroscopy and NMR, Michelson interferometer, Instrumentation of UV-Vis,
IR, Fluorescence Spectrometer Atomic Spectrometry- Atomization, Flames,
furnaces and plasmas, Temperature Effects on Atomic spectroscopy, Inductively
coupled Plasmas, Hollow Cathode Lamp, Interferences, Isobaric Interference Back
ground Correction techniques, Mass Spectrometry, Ionization Methods Types of
Mass Spectrometer, Quadrupole Spectrometer, Time of Flight, Orbitrap, Ion
Mobility Mass Spectrometer Chromatography Mass Spectrometry Hyphenated
methods, Introduction to ICPMS, XPS.
References:
1. Harris, D. C “Quantitative Chemical Analysis”, 8th Edition, 2010, WH Freeman and Company, New York.
2. Hatakeyama, T. and Quinn, F. X. “Thermal Analysis”, John Wiley&Sons, 1999.
3. Settle, F. A., “Handbook of Instrumental Techniques for Analytical Chemistry”, Pearson
4. Skoog, D. A. West, D. M. and Holler, F. J. "Fundamentals of Analytical Chemistry", 9th Edition, 2014 Saunders
5. Vogel, I. “A Textbook of quantitative Inorganic Analysis”, 5th Edition 1989, Longman.
6. Wendladt, W.W. Thermal Methods of Analysis, Interscience, 1964.
7. Willard, L. L., Merit H. H. and Dean, J. A. "Instrumental Methods of Analysis", Affiliated East-West 5th Edn., Van
Nostrand, 1974.
8. Farhataziz and Rodgers, M. A. J. Radiation Chemistry: Principles and Applications VCH Publishers, New York
(1987).
th
9. Arnikar, H. J “Essentials of Nuclear Chemistry”, , Wiley Eastern Limited, 4 Edition.(1995)
10. Christian, G. D. O’Reilly, J. E. Instrumental Analysis, Allyn&Bacon, 1986.

Additional references:
11. Day, R.A and Underwood, A. L. Quantitative Analysis, Prentice Hall, 1967.
12. Ehmann, W. D. and Vance, D. E Radiochemistry and Nuclear methods of analysis, John Wiley (1991)
13. Fifield, F.W. Kealey, D. Principles and Practice of Analytical Chemistry, Blackwell
14. Friedlander, G. Kennedy J. W. and Miller J. M. Nuclear and Radiochemistry, John Wiley (1981)
15. Kennedy, J. H. Analytical Chemistry: Principles, Saunders College Pub., 1990.
16. Kolasinski, K.W. Surface Science: Foundations of Catalysis and Nanoscience, 2nd Edn., Wiley, 2009.
17. Mermet, J. Otto, M. Kellner, M. R. Analytical chemistry, Wiley-VCH, 2004.
18. Wilson, C. L. Wilson, D. W. Comprehensive Analytical Chemistry, Elsevier, 1982.

Model Question Paper

FOURTH SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-DE-544: ANALYTICAL ANDINSTRUMENTAL METHODS

83
Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Write down significant figures of i)0.0009 Kg ii) 9.50 mm iii) 85000


iv) 4.5600 X 104
2. Plot a titration curve for the titration between a strong acid vs strong base. Which
indicator can be used for this titration?
3. Explain a method to separate polymers according to their size.
4. How can two stereoisomers of a compound be separated?
5. Enumerate the methods to improve S/N ratio while handling instruments.
6. Why are FETs also known as unipolar transistors?
7. What is the principle of neutron activation analysis?
8. How does positron emission tomography work?
9. Depict a cyclic voltammogram and explain completely.
10. What is meant by fourier transformation in IR or NMR?
11. Explain MALDI and FAB mass techniques.
12. Differentiate between DSC and DTA.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. What is meant by distribution of random errors? Explain


14. Discuss the principle and application of any one electrokinetic separation method.
15. What technique is used to determine polydispersity indices?
16. What are hyphenated techniques? Give the principle of any two.
17. What are the techniques to measure radioactivity?
18. Explain the difference between SEM and TEM.
19. What are the different types of optical sensors and what are their applications?
20. What are the temperature effects on atomic spectroscopy in general?

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21. Explain various ways to minimize the errors encountered during an analysis.
22. Explain the various thermoanalytical techniques that can be used to study the thermal
properties of a material.
23. Explain the working of nuclear fission and fusion reactors.
24. Compare the techniques EDX, XPS, AAS and ICPMS.

84
1. Semester 1
2. Course Title ANALYTICAL AND
ENVIRONMENTAL CHEMISTRY
3. Course Code CHE-GC-501
4. Credits 2
5. CO TL KL PSO
On completion of the course, students should be able to: No.
1. Understand the basics of data analysis and titrations 1-R, FK, CK I, II
2-Un,
3-Ap
2. To understand the practice of titrations and volumetry 2-Un, FK, CK I, II, III
3-Ap
4-An
3. Comprehend the theory of chromatography and understand the various 1-R, FK, CK I, III
chromatographic methods 2-Un
4. To know the science behind the various environment phenomena like 2-Un, FK, CK I, II, III
greenhouse effect, acid rain etc 5-E
5. To know about various types of pollution 2-Un, FK, CK II, III
3-Ap
6. To understand solid waste management issues 2-Un, CK III
3-Ap
MODULE COURSE CONTENT CO No.
No
I Data Analysis - Accuracy and precision. Evaluation of analytical data, The 1
mean and median. Standard deviation, variance and coefficient of variation.
Classification of errors. Minimization of errors. Significant figures and
computations. Statistical methods in analysis. Students T test, Rejection of
suspected value, Q test.

II Volumetric Analysis and Precipitation Methods - Classification of reactions 1, 2


in volumetry (titrimetry). Acid-base equilibria in water. Buffers. Titration
curves. Theories of indicators. Theory of complexometric titrations and
applications, Solubility product. Common ion effect. Super saturation and
precipitate formation. Precipitation from homogeneous solutions. The purity
of precipitate. Co-precipitation and post precipitation. Contamination of
precipitates. Washing of precipitate. Ignition of precipitate. Organic
reagents used in gravimetry
III Chromatographic Methods: Principles, instrumentation and applications of 3
column chromatography, paper chromatography, thinlayer chromatography,
ion-exchange chromatography, Gas chromatography and HPLC. Detectors,
Hyphenated techniques, Introduction to Chiral Chromatography, Molecular
Exclusion Chromatography, Introduction to Method development and
Analysis of samples using the above techniques.
IV Introduction to Environmental Chemistry - Components of Environment. 4
85
Earth’s atmosphere, Stratosphere chemistry, Ozone formation and depletion,
Protection of ozone layer, Chlorofluorocarbons, Chemistry of photochemical
smog, Acid rain, Atmospheric production of nitric acid, sulphuric acid, Rain,
snow and fog chemistry, Aerosols, Adverse effects of acid rain, Green house
effect. Impact of greenhouse effect on global climate.

V Air and Water Pollution - Air pollution incidents. Control measures for air 5
pollution. Water pollution, Incidents of water pollution in India – examples
– causes, effects and remedial measures, Case studies, Humic material,
Metal complexes of ligands of anthropogenic origin, Soaps and detergents.
Eutrophication.

VI Solid Waste Management - Heavy metals. Industrial waste water treatment: 6


Solid wastes from mining and metal production, Organic wastes, Mixed
urban wastes, Solid waste management, Pollutants in soil. Radioactive
pollutants. Pollutants from industries and agriculture. Chemical toxicology.
Biochemical effects of pesticides and heavy metals.

References

 Bailey, R. A. Clark, H. M. Perris, J. P. Krause, S. and Strong, R. L. “Chemistry of the


Environment”,Academic.
 De, A. K. “Environmental Chemistry”,Wiley Eastern.
 Manjooran,K. B. “Modern Engineering Chemistry”, Kannatheri Publications, Kochi.
 Skoog,D. A. West, D. M. and Holler,F. J. "Fundamentals of Analytical Chemistry", Saunders
 Sodhi,G. S. “Fundamental Concepts of Environmental Chemistry”, Narosa.
 van Loon, G. W. “Environmental Chemistry”, OUP.
 Vogel, I. "A Textbook of Quantitative Inorganic Analysis", Longman.
 Wilson, C. L. and Wilson,D. W. “Comprehensive Analytical Chemistry”, Vol. IB

Model Question Paper

FIRST SEMESTER M.Sc. DEGREE EXAMINATION 2020


Branch: CHEMISTRY
CHE-GC-501: ANALYTICAL AND ENVIRONMENTAL CHEMISTRY

Time: 3 hours Max. Marks: 60

SECTION-A
Answer any 10 questions. Each question carries 2 marks

1. Write down significant figures of i)0.0009 Kg ii) 9.50 mm iii) 85000


iv) 4.5600 X 104
2. Calculate the mean and median for the data: 17.4; 17.5; 17.6; 17.8; 18.1; 18.3
3. Exemplify the concept of common ion effect.
4. Plot a titration curve for the titration between a strong acid vs strong base. Which
indicator can be used for this titration?
5. Explain a method to separate polymers according to their size.

86
6. How can two stereoisomers of a compound be separated?
7. Explain the photochemical smog phenomenon.
8. What are the chief greenhouse gases present in our atmosphere?
9. What are the control measures for air pollution?
10. Differentiate between soaps and detergents
11. What are the main sources of heavy metal pollution?
12. Explain the term “chemical toxicology”.

SECTION-B
Answer any 6 questions. Each question carries 4 marks

13. What is meant by distribution of random errors? Explain.


14. Write a note on any three organic reagents used in gravimetry.
15. Briefly mention the theory of acid-base indicator.
16. What are hyphenated techniques? Give the principle of any two.
17. How can thin layer chromatography be carried out? Explain.
18. Explain how ozone is formed and decomposed in the atmosphere.
19. What are the causes, effects and remedial measures for water pollution?
20. What are the major solid waste management strategies?

SECTION-C
Answer any 2 questions. Each question carries 8 marks

21.Explain various ways to minimize the errors encountered during an analysis.


22. What are the organic precipitants generally employed in gravimetry ? Discuss.
23. Explain greenhouse effect and acid rain.
24. Explain the biochemical effects of pesticides and heavy metals.

87

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