Oct/Nov 07 Analysis 1) Light source X emit light of higher energy than light source Y a) Which has longer ?

? b) Which has higher frequency ? (2m) 2) Calculate the % of the incident radiation absorbed by a sample with an absorbance of 0.1 (2m) 3) What is the concentration of Carbimazole [ A(1%, 1cm) = 557 at 291nm ] if the measured absorbance at 291nm is 0.557 ? Give your answer in g/100ml (2m) 4) Explain why absorbance values of more than 1 are not usually acceptable when quantifying the content of a drug in a given sample (2m) 5) Explain what you understand by the following terms: a) Internal conversion (2m) b) Interstate crossing (2m) Illustrate your answer clearly with the aid of labelled diagram if necessary 6) State 2 ways by which the fluorescence intensity of a given concentration of a compound could be increased (4m) 7) A non basic compound, C8H9NO, gave an infrared spectrum showing the following major absorption bonds: 3030, 1689, 1600, 1520, 1439, 1370, & 690nm-1. Interpret these data in terms of a plausible structure for the compound (4m) 8) What is the fingerprint region of an infrared spectrum & how can it be used for pharmaceutical analysis? (2m) 9) Discuss 2 sample preparation technique for atomic absorption spectroscopy (4m) 10) The assay of the weakly basic antibacterial agent, metronidazole, involves non-aqueous titration using perchloric acid ( HClO4)

a) Write the chemical equation for the reaction between metronidazole & perchloric acid (2m) b) Give a suitable solvent for this assay (1m) c) Suggest 2 reasons why aqueous titration cannot be used for the assay of metronidazole? (2m) 11)a) In the term NMR spectroscopy , what does the abbreviation NMR stand for ? (1m)

b) What is meant by diamagnetic shielding (diamagnetic anisotropy)?

(3m)

12)a) Explain briefly why coupling occurs in a H-NMR spectrum (2m) b) Draw the splitting pattern of peaks that can be observed in a H-NMR spectrum of a sample of ethanol contaminated with a drop of acid. Make sure the relative size of each set of the peaks corresponding to the relevant no of protons (4m) 13)a) Why is the intensity of the signal for a 4o carbon in the 13C-NMR spectrum very weak? (2m) b) What is the disadvantages of proton-decoupling in a 13C-NMR spectrum? (2m) 14) What is DEPT experiment and what are its uses? (4m)

15) Write short note on the 3 basic function of a mass spectrometer. (5m)

16a) Explain why the molecular ion (M+) peaks of alcohols are rarely seen in their electron impact mass spectra. (2m)

16b) What is the ionisation technique that can be used to produce a molecular ion (M+) ion peak? (1m)

17a) Based on the procedure below. Determine the concentration of haloperidol in the injection solution. (5m) (i) (ii) (iii) (iv) (v) Add 15 ml of 1 M HCl to 5 ml of haloperidol injection solution. Extract 3x with ether. Wash the combine ether extracts with 10 ml of H20. Combine the aqueous layer and dilute to the 100 ml. Take 10 ml of the diluted aqueous solution and dilute to 100 ml. Read the absorbance at 245 nm, which gives 0.873 [A(1%, 1 cm) at 245 nm = 346].

17b) Discuss 2 quarantine method in uv-vis spectrophotometry, which can be used to overcome interference in drug analysis. Illustrate your answer clearly with one suitable example for each method. (4m)

17c) Explain the following term in electronic spectrometry. Give example to illustrate your answer. (4m) (i) Auxochrome

(ii)

Hypsochromic shift

17d) Explain why the following compound have different max . Illustrate your answer. (3m)

max = 177 nm

max = 183 nm

18a) Describe the main principle of IR absorbtion by organic molecule, including the different type of vibration associated with it. (6m)

18b) Assign the streching frequency of the following group to their respective region in the IR spectrum (500-4000 cm -1 ) and explain their relative position using the simple harmonic motion model (= / ) (4m) C C

C=C

C-C

C-H

C=O

C-O

O-H

N-H

18c) Give the wave number for the major absorption bands in the IR spectrum of paracetamol given below (obtained using the KBr disc method) together with the corresponding functional group. (3m)

paracetamol

18d) Briefly describe the procedure for the preparation of a KBr disc and the advantages of the KBr disc method compared to the nujol mull method. (4m)

18e) Discuss how you can differentiate the following compound based on the OH strecthing band. (3m) O O C CH3 OH