PHARMACEUTICS DEPARTMENT HUBLI

K.L.ES COLLEGE OF PHARMACY

MODERN PHARMACEUTICAL ANALYSIS

YEAR

UV/VISIBLE SPECTROSCOPY
Explain the basis of visible & uv spectroscopy of organic compounds? Explain the fundamental laws relating the absorption of EMR to the concentration of the solute The l max of the following dienes differs with 10nm state which has a higher max & why

MARKS

Nov 97

10

Nov 97

Nov 97

July 98 July 98 July 98 July 98 July 98

Sep 99 2000 2001

2001 2002 2002 2002

Give a brief account of a) molecular excitation coefficient b) factors which causes bathochromic shift c) effect of solvent on the max Discuss the various types of electronic transition that occur when a compound is irradiated with EMR Describe spectrophotometer titrations with examples Explain wood wards rules & its application State wood wards rules & illustrate their applications in structural analysis in giving examples Enumerate & explain the different types of electronic transition produced in organic compounds by the UV absorption & arrange them in the order of increasing order State the difference between molecular & electronic spectra & explain their origin in organic compound Interaction of EMR with UV & IR Explain the modes of electronic excitation. Depict the various regions of the EMR giving their corresponding wavelength & show portion can bring about the electronic transition State & explain Beers-Lamberts law & show how it is useful in quantitative analysis Explain the interaction of EMR with molecules in UV/IR Note on detectors employed in UV/IR spectrophotometer How will you differentiate between the following 2 Compounds of a pair on the basis of UV & IR spectra? Give appropriate absorption wavelength values in both UV & IR spectra? Give appropriate absorption wavelength values in both UV & IR spectra

8 10 7 12 5

8 5 8

8 5 5

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PHARMACEUTICS DEPARTMENT HUBLI 2002 2003 2003 2003 2003 2004 2006

K.L.ES COLLEGE OF PHARMACY 5 10 8 13 12 10 20

Describe the different radiation sources & monochromators generally employed in UV visible spectrophotometer Explain the principle of absorption spectra by molecules in UV-visible region Sample handling in UV & IR spectroscopy Write about Woodward rules & its application in characterization of substances Discuss the factors which affect shifts in UV visual spectroscopy Define Beers-Lamberts law. Derive mathematical expression for law. Add note on deviation of the law Why are the absorption bands in a UV spectrum very broad when compared to IR or NMR spectra? What are the factors that govern the position & intensity of the absorption bands in UV spectrum? Give the analytical application of UV visible spectrophotometry Explain Woodwards rule for prediction of max in dienes Discuss the theory of UV visible spectroscopy Outline the utility of absorption spectroscopy in the qualitative & quantitative analysis

2006 Apr 2007 Apr 2007 NOV 97 Nov 97

5 10 10

INFRARED SPECTROSCOPY
What is meant by finger print region in an IR spectrum discuss its importance in the identification of organic compounds How will you differentiate the following pairs of compounds using IR spectra 5 6

1) 2) PhCOCH2CH3 & PhCH2COCH3 3)

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PHARMACEUTICS DEPARTMENT HUBLI Nov 97 Nov 98 Sep 98 2001

K.L.ES COLLEGE OF PHARMACY 9 5 9 9

Discuss the samples handling in IR spectroscopy Justify the statement the carbonyl region in IR spectrum is most informative citing suitable ex Explain the characteristic IR spectral feature of aromatic ring, alkynes, esters How can the following compounds be distinguished based on their IR spectra a) phenyl acetone & propiophenone b) benzyl chloride & benzoyl chloride c) Cis-stibline & trans stibline Explain theoretical basis of IR Different types of detectors in IR Distinguish the following using IR a) primary & secondary amines b) aliphatic aldehydes & ketones c) aromatic & aliphatic compounds d) Intermolecular & intermolecular hydrogen bonding Distinguish the following using IR a) Cis & trans butene b) cyclohexane & benzene c) Benzaldehyde & Benzophenone Detectors used in IR SPECTROSCOPY Discuss the general appearance of IR spectrum of a normal alkane. What are the changes in the above spectrum seen upon introduction of following structural residues alkene, alcoholic-OH, carbonyl Primary amines shows doublet peak at the region B/N 3100-3500 cm-1 in IR What is Fermi resonance? Explain the factors affecting the absorption position in IR spectroscopy Why C=0 str of amides is observed at lower wave number than c=0 str of acids in IR

2002 2002 2002

6 9 10

2003

2004 2006

10 20

2006 2007 2007 why July 98 Nov 98

5 10 5

OPTICAL ROTATORY DISPERSION

What is optical rotatory dispersion & how is it useful in characterization of substances What is meant by ORD ? discuss the principles & applications of ORD 9 13

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PHARMACEUTICS DEPARTMENT HUBLI 2000 2004 2004 2005 2006 ORD & circular dichroism Cotton effect

K.L.ES COLLEGE OF PHARMACY 5 9 20 10 5

Note on the principle & application of ORD & circular dichroism Write an account on fundamental principles of ORD Explain circular dichroism

NUCLEAR MAGNETIC SPECTROSCOPY

1997 1997 1997 Draw a typical P.M.R spectrum & explain its characteristics giving all the conventions & notations used in describing the spectrum Discuss the origin of splitting phenomenon in the P.M.R spectrum of organic compounds and their significance in structural diagnosis Explain the meaning & significance of the following terms with reference to NMR spectroscopy a) Chemical shift b) Magnetic anisotropy c) Spin-Spin coupling d) NOE effect e) Lanthamide Shift reagents Predict the approximate chemical shift & signal multification for the following a) CH3-CH2-O-COO-CH3 b) H3CO-C6H4-COO-CH3 Explain the advantages & applications of FTNMR What is spin-spin coupling & decoupling? explain with ex Show the important components of NMR Spectrometer in a neat diagram & explain their functions Draw a typical N.M.R spectrum & explain its characteristics giving all the conventions & notations used in describing the spectrum Principle & applications of C13 NMR Spectrometry Explain the chemical shifts & splitting pattern expected in each of the following a) Vinyl methyl Ketone b) 1-Chloro-2-bromo ethane c) 4-Methoxy benzoic acid d) Acetophenone Explain the meaning & significance of the following terms in NMR spectrometry a) Isotropy & anisotropy b) Coupling constant 10 7 15

1997

10

1997 1998 1998 1998 1998 1999

5 8 8 8 5 12

1999

13

PHARMASTORM@YAHOO.CO.IN

PHARMACEUTICS DEPARTMENT HUBLI

K.L.ES COLLEGE OF PHARMACY

2000 2000 2000 2001 2001

c) Spin-Spin relaxation d) NOE effect Explain chemical shift. Write a note ob NMR resonance of protons on heteroatoms O,N&S What is coupling constant? Discuss factors influencing coupling constant Short note on C13 NMR Describe the theoretical basis, principle of operation & applications in structural analysis of PMR spectroscopy What is meant by time domain & frequency domain curves? How can the former be converted into the latter? What are the advantages of such conversion Explain the theoretical basis of proton NMR Spectroscopy Give a short account of pulsed NMR Spectroscopy Explain a brief account of 2DNMR technique Write a note on C13 NMR spectroscopy Discuss factors affecting chemical shift with suitable ex Explain chemical shift in NMR Discuss proton NMR of hetero atom like O,N,S. Diagram & explain NMR of an absolute alcohol Spin-Spin coupling & decoupling Explain the technique used for decoupling the interaction between 13C NMR & 1H interaction in carbon -13 NMR What is magnetic anisotropy? Explain with ex How many NMR signals will arise from acetaldehyde Outline the theory of PMR spectroscopy What is spin-spin splitting? Give the rules that characterise the spin-spin splitting of PMR resonance peak What is decoupling? What is its significance in 13C spectroscopy a) Describe the concept of NMR Spectroscopy. What are the factors affecting chemical shifts b) What are Decoupling methods? what is its significance in 13C spectroscopy What is chemical shift? What are the factors affecting chemical shift? Give ex What is the scope of decoupling methods in 13C spectroscopy a) b) a) b)

10 7 5 18 7

2002 2002 2002 2003 2003 2003 2003 2004 2004 2005 2006

9 8 5 7 8 5 5 12 20 10 20

2006 2006

10 20

2007 2007 1997 1997 1997 1997

10 10 8 7 5 10+6+9

MASS SPECTROSCOPY
Outline the basic theory of mass spectroscopy General rules of fragmentation of organic compounds Write a note on Mc Lafferty rearrangement a) Discuss the principles of operation of a mass Spectrometer b) Enumerate & explain the different methods of ionization of samples in

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PHARMACEUTICS DEPARTMENT HUBLI

K.L.ES COLLEGE OF PHARMACY

1998 1998 1998 1998 1998 1998 1998 1999 2000 2000 2000 2001 2001 2001 2003 2003 2003

2004 2004

mass spectrometry & their applications c) Give a brief account of 1) Metastable peaks 2) Nitrogen rule 3) Mc Lafferty rearrangement Explain the principle & working of a mass spectrometer Discuss the various factors affecting fragmentation with suitable ex Write a note on fast atom bombardment mass spectroscopy Discuss he principle involved in the functioning of magnetic deflection, time of flight & quadruple mass spectrometers Explain the general rules for fragmentation of organic compounds What are the likely fragments expected in the mass spectrum of 1) Benzyl chloride 2) Methyl benzoate 3) Hexane-2-one Explain the chemical shift & splitting pattern expected for 1) ethyl benzene 2) 1-Bromo-2chloroethane 3) Vinyl methyl ketone Explain Nitrogen rule & Metastable ions Name the general rules & rationalisation employed for predicting prominent fragment peaks in electron impact spectra. Give ex What are the various techniques used to produce ions of proteins Write a note on chemical ionisation Describe the main component of a mass spectrometer & their functioning a neat sketch Explain the general the importance of M, M+1, M+2 peaks Explain the general rules for fragmentation of organic molecules under electron impact conditions Outline principle of mass spectrometry Write about Mc Lafferty rearrangement Indicate the points of bond rupture in the molecule which would lead to each major mass fragment a) 2-methyl-2-butanol which has peaks of appreciable intensity at m/e=73,59,55 b) Tert-butylacetate with peaks at m/e=101,59,57,43 Explain the principle of mass spectrometry Outline the fragmentation pattern of

10 9 6 13 6 6 9 5 10 5 5 7 8 10 10 7 8

5 6

2004

2004

Explain the following with respect to mass spectrometry a) Molecular ion & its use b) Metastable ion c) Mc Lafferty rearrangement Explain the characteristics of isotope peaks in mass spectra

3+2+5

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PHARMACEUTICS DEPARTMENT HUBLI 2005

K.L.ES COLLEGE OF PHARMACY 10+10

2005 2006 2006

2006 2006 2006

2006 2006 2007

2007

Explain the following a) What is the function of analyser in mass spectrometer? Name the common analyser used b) Explain in detail the fragmentation rules in electron impact MASS SPECTROMETRY. Give suitable ex Write fragmentation patterns resulting in Peeks in the mass spectra of ALLYI-ISOPROPYL-ETHER Outline the instrumentation of mass spectrometry with special reference to different types of mass analyser Write notes on a) Mc Lafferty rearrangement b) Isotopic effects in mass spectroscopy Write mass fragmentation patterns & NMR split patterns for the organic molecules a) Phenyl acetic acid b)Isobutyl chloride With an ex the concept of Ring rule Explain the following concepts a) Fermi resonance b) Fast atom bombardment mass spectroscopy c) Millers indices Chemical ionization spectra is useful in obtaining molecular Wt of organic compounds rather than Electron impact ionization spectra Explain the rules of fragmentation in mass spectroscopy with one characteristic ex each Write a note on a) Recognition of molecular ion peak b) Mol wt & mol formulae determination for a compound from its mass spectrum c) Interpretation of mass spectra Write mass spectral fragmentation patterns & NMR spectral features for the spectral data a) Maleic acid from Furmic acid b) Salicylic acid from P-hydroxy fenzoic acid

5 12.5 12.5

10 5 10

5 10 5+5+10

10

PHARMASTORM@YAHOO.CO.IN

PHARMACEUTICS DEPARTMENT HUBLI

K.L.ES COLLEGE OF PHARMACY

PHARMASTORM@YAHOO.CO.IN