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AS/APR 2010/CHM580

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

SPECTROCHEMICAL METHODS OF ANALYSIS CHM580 APRIL 2010 3 HOURS

INSTRUCTIONS TO CANDIDATES 1. 2. 3. This question paper consists of six (6) 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) iii) the Question Paper a four - page Appendix - provided by the Faculty an Answer Booklet - provided by the Faculty

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

This examination paper consists of 7 printed pages
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QUESTION 1 a) Calculate the frequency, the wave number and the energy associated with the 5.715 urn vibrational absorption band of an aliphatic ketone. (2 marks) Explain why the transmitted radiation, P, is always less than the radiation, P0, incident onto a cuvette, even if there is no absorption of radiation by the contents of the cuvette. (2 marks) Compare the following i) hydrogen and deuterium lamps. (1 mark) ii) conventional and diode array spectrophotometers. (2 marks) d) A monochromator is one of the components of an optical instrument. i) What is the function of a monochromator? (1 mark) ii) Explain why a monochromator is the best choice in an optical instrument to be used for the function mentioned in (i) above. (2 marks) e) Deviations from Beer's Law become noticeable at high concentrations of samples. i) How would the absorbance-concentration plot deviate from Beer's Law at high concentrations and why does this deviation occur? (2 marks)

b)

c)

ii) If you were analyzing a relatively concentrated solution, what can you do to bring the absorbance level into the linear Beer's Law range without changing the concentration of solution? Justify your answer. (2 marks)

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QUESTION 2 a) Flame and electrothermal vaporizer are atomizers for atomic absorption spectroscopy (AAS). i) Compare the signal produced from flame atomic absorption spectroscopy (AAS) to electrothermal AAS. (3 marks) ii) Which technique in a (i) is expected to have a lower detection limit? Explain. (3 marks) iii) Give one other advantage and disadvantage of each method. (2 marks) b) Describe the basic principles and requirements of a hollow cathode lamp in AAS and a plasma in inductively coupled plasma (ICP), (4 marks)

c) Spectral and chemical interferences are encountered in atomic absorption methods i) Describe the two types of interference. (3 marks) ii) Give two examples of chemical interference. (2 marks) iii) Name one method that could be used to correct for each of these interferences in part d ii) and describe how each method works to correct for the corresponding interference. (4 marks) d) A gas is flowed through the graphite furnace during operation. Name the gas used for the purpose. Does this flow occur during all three step processes in the electrothermal cycle? If not, specify which steps and explain. (3 marks) e) Describe two reasons why an ICP torch is better than a flame for multi-element emission. (4 marks)

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f)

Analysis by flame AAS was conducted on an archeological sample consisting of pottery fragment for cadmium. The 2.2319 g shard sample was digested by addition of 2 mL of 40% HF and 2 mL of 65% HN0 3 . This sample was then diluted to 25.00 mL with deionized water. Aliquots of 1.0 mL of treated sample were added to five 10.0 mL volumetric flasks. The following volumes of 200 ppm Cd(N0 3 ) 2 standard solution were added followed by dilution to the 10.0 mL mark. The flame AA signal were measured for each and summarized below. Volume of standard solution (mL) 0 1 2 3 4 Signal 0.156 0.272 0.397 0.511 0.626

A plot of absorbance against volume of added standard produced a linear relationship, y = 0.1179x +0.1566. Calculate the percentage of Cd in the pottery fragment. (4 marks)

QUESTION 3 a) The structures of the principal male and female sex hormones, testosterone and estradiol are shown below. Ultraviolet-visible (UVA/is) spectrometer is used to determine the concentration of the hormones. OH OH

Hcr

Testosterone

Estradiol

i) Explain the principles of UVA/is absorption by these molecules. (3 marks) ii) What are the transitions for the UVA/is absorption of testosterone? (2 marks) b) Explain how infrared (IR) spectroscopy is useful in identifying the molecular structure and the limitations for its use in structure elucidation. (4 marks)

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AS/APR 2010/CHM580

c)

Distinguish between Stokes and anti-Stokes lines. Why are anti-Stokes lines less intense than Stokes lines? (4 marks)

d) Why is spectrofluorometry potentially more sensitive than spectrophotometry? (3 marks)

QUESTION 4 a) In nuclear magnetic resonance (NMR) spectroscopy, define and illustrate the chemical shift parameter. (3 marks) The 1H chemical shift of ethylene at 8 5.27 is at about the middle of the proton chemical shift range. Indicate, relative to ethylene, approximately where the following proton types would resonate i) A proton which is more shielded relative to ethylene. (2 marks) ii) A proton which is down field from ethylene. (2 marks) iii) A proton that is on a carbon with more s character. (2 marks) c) Indicate how many nonequivalent peaks can be observed in the 13C NMR spectrum of each compound in the following set:

b)

(6 marks)

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QUESTION 5 State the advantages of a) FT-NMR measurement over a continuous wave (CW) measurement in NMR spectroscopy. (3 marks) Electron impact (El) over Field Ionization (Fl) or Chemical Ionization (CI) sources in mass spectrometry. (3 marks) Describe two applications of MS or GC-MS or NMR technology in Magnetic Resonance Imaging in either forensic science, environmental analysis or clinical applications. (2 marks)

b)

c)

QUESTION 6 Compound D has the formula C9H120. The 13C NMR spectrum shows peaks at 28, 31 57, 122 124, 125 and 139 ppm. The IR and NMR spectra are shown below. a) Calculate the index of hydrogen deficiency for the compound. (2 marks) b) What functional groups do the index and IR spectrum indicate? (2 marks) c) What is the ratio of protons as you go from upfield to downfield in the 1H NMR spectrum and what information does it give? (3 marks) What does the 13C NMR indicate? (3 marks) e) Determine the structure of the Compound D. (5 marks)

d)

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END OF QUESTION PAPER

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