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AS/APR 2011/CHM580

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

SPECTROCHEMICAL METHODS OF ANALYSIS CHM580 APRIL 2011 3 HOURS

INSTRUCTIONS TO CANDIDATES 1. 2. 3. This question paper consists of nine (9) questions. Answer ALL questions in the Answer Booklet. Start each answer on a new page. Do not bring any material into the examination room unless permission is given by the invigilator. Please check to make sure that this examination pack consists of: i) ii) Hi) iv) the Question Paper an Answer Booklet - provided by the Faculty a Graph Paper - provided by the Faculty IR, NMR and Mass Correlation Charts - provided by the Faculty

4.

DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO

This examination paper consists of 8 printed pages
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AS/APR 2011/CHM580

QUESTION 1 a) An argon ion laser operates at 496.5 nm. i) What is the wavenumber of the laser at 496.5 nm? (1 mark) ii) What is its frequency? (1 mark) b) Lasers are used as sources in many of the spectroscopic instruments. Identify ONE such method and indicate what analytical advantage the use of a laser contributed to the method. (2 marks) Sketch, label and state the functions of the components of a grating monochromator. Explain why monochromators are widely used in current spectrometers. (6 marks)

c)

QUESTION 2 a) Explain the differences between the following agents used in atomic absorption and emission spectroscopy i) releasing agent ii) protective agent iii) ionization suppressor (3 marks) b) Why is source modulation employed in atomic absorption spectroscopy? (2 marks) c) Inductively coupled argon plasma emission intensities are typically linear with concentration over a few orders of magnitude, whereas atomic absorption measurements are linear typically over a very limited range. Explain. (3 marks)

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d)

Refer to the diagram below

i) Name the object shown in the diagram. Be specific. (1 mark) ii) Explain the advantage of the long slot. (2 marks) iii) How and where is the sample introduced? Explain the processes which occur when the sample is introduced. (3 marks) iv) What is the potential danger associated with this part of the instrument? How can it be dealt with? (2 marks)

QUESTION 3 a) Describe standard addition and discuss why this calibration method should be employed in an analysis. What type of sample is standard addition method preferably used? (3 marks) The data below are the detection limits of potassium and silver in ppb determined for Flame AAS, GFAAS and ICP-OES in a task of establishing the detection limits for the two elements using atomic spectroscopy. Clearly explain the trends in the data, including why the trends for the two elements are different. Element K Ag Flame AAS 1 0.9 GFAAS 0.004 0.001 ICP-OES 30 0.2 (4 marks)

b)

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QUESTION 4 a) Draw a schematic diagram showing components of a single beam photometer for absorption measurements in the visible region. (4 marks) Describe the major advantages of double beam as compared to single beam instruments for UV-visible absorbance measurements. (2 marks) A compound of formula weight of 280 g mol"1 absorbed 85.0% of the radiation at a certain wavelength in a 2.5 cm cell at a concentration of 15.0 ug ml_"1. Calculate its molar absorptivity at the wavelength. (3 marks)

b)

c)

QUESTION 5 a) i) Why is spectrophotometry less sensitive than spectrofluorometry? (2 marks) ii) Explain why heterocyclic compounds such as furan as shown below do not exhibit fluorescence.

o
furan (2 marks) b) Fe2+ is determined spectrochemically by reacting with 1,10-phenanthroline to produce a complex that absorbs strongly at 510 nm. A stock standard Fe2+ solution is prepared by dissolving 0.0704 g ferrous ammonium sulphate, Fe(NH4)2S04.6H20 (392.14 g mol"1), in water in a 1000 ml_ volumetric flask, adding 2.5 mL H 2 S0 4 and diluting to mark. A series of working standards is prepared by transferring 1.00, 2.00, 5.00 and 10.00 mL aliquots of the stock solution to separate 100 mL volumetric flasks and adding hydroxylammonium chloride solution to reduce any Fe3+ to Fe2+, followed by phenanthroline solution and then dilution to volume with water. An unknown sample is prepared by adding the same amount of reagents in a 100 mL volumetric flask and diluting to volume. If the following absorbance readings measured against blank are obtained at 510 nm, calculate the molar concentration of the unknown sample. (8 marks) Solution Standard Standard Standard Standard Sample Hak Cipta Universiti Teknologi MARA A 0.081 0.171 0.432 0.857 0.482 (8 marks) CONFIDENTIAL

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AS/APR 2011/CHM580

QUESTION 6 a) The most common detector used in FTIR is TGS (Triglycine sulfate) detector which is a thermal detector. Explain why a photon detector cannot be used in FTIR spectrometer. (3 marks) b) Explain why a FTIR spectrometer will give spectra having a better signal-to-noise ratio than a dispersive IR spectrometer. (2 marks) c) IR spectra and Raman spectra can give information about the same vibrational energy transitions in a molecule. i) Describe and sketch an energy diagram to show the transitions and processes that are important in vibrational spectroscopy. (6 marks) For a particular vibrational change, what requirements must be met in order to observe an IR absorption and a Raman shift? (4 marks)

ii)

QUESTION 7 a) Describe how to distinguish between propanone, pentane-2-one and pentane-3-one by mass spectrometry. Explain using fragmentation of each. (6 marks) b) Calculate the m/z and relative abundance (intensity) for the M+ and (M+ + 1) peaks for 2-chloropropane. Assume the molecular ion to be the base peak in each case. (3 marks) c) State the advantages and disadvantages of an electron impact source. (3 marks) d) Give two applications of molecular mass spectrometry. (2 marks)

QUESTION 8 a) Why a superconducting magnet is used in a high resolution NMR spectrometer? (1 mark) b) What type of solvents is used in NMR? Why? (1 mark)

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c) What are the purposes of locking and shimming in a NMR operation? (2 marks) d) i) What is meant by 'chemical equivalence' in NMR? (1 mark) ii) C3H6CI2 gives only ONE signal in its 1HNMR spectrum. Propose the structural formula. (3 marks)

QUESTION 9 The IR, mass, 1H NMR and 13C NMR spectra shown below are for a compound with the formula of C7H1402. What is the structure of the compound? Justify your answer. (9 marks) IR spectrum

HfNENWIBEHl-il

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Mass spectrum

H NMR spectrum
Doublet, J= 6

Doublet, J = 2.0

Quartet, J =1.

11

-]'r 10 9

HSP-00-116

ppm

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13,

C NMR spectrum

200
CDS-03-419

ppm

END OF QUESTION PAPER

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