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AS/OCT 2010/CHM580

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

SPECTROCHEMICAL METHODS OF ANALYSIS CHM580 OCTOBER 2010 3 HOURS

INSTRUCTIONS TO CANDIDATES 1. This question paper consists of two (2) parts : PART A (3 Questions) PART B (3 Questions)

2.

Answer ALL questions from PART A and PART B into two (2) different Answer Booklets. 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) iv) the Question Paper an Answer Booklet - provided by the Faculty a Graph Paper - provided by the Faculty an Uv-vis/NMR/IR table - provided by the Faculty

3.

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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PART A

QUESTION 1 a) Briefly define the following terms: i) absorption ii) spectrophotometer iii) Beer's law (3 marks) b) In hexane, acetone has an absorption maximum at 270 nm, where its molar absorptivity has a value of 12 M"1 cm"1. Our spectrometer can reliably measure transmittance between 10% and 90%. What is the range of acetone concentration that can be measured in a 1.00-cm cell under these circumstances? (5 marks) c) Sketch and describe the instrumental components of an ultraviolet-visible spectrophotometer. Outline the physical principles behind its operation and specify any limitations to its operation. (8 marks) d) Explain and relate the following terms below as used in the ultraviolet-visible spectroscopy: i) Bathochromic shift ii) Hypsochromic shift iii) Auxochrome (3 marks) e) A spectrophotometric assay was undertaken with a substance with a molar absorptivity of 4000 M"1 cm"1. A stock solution is available whose concentration is 0.0195 M. The instrumental path length is 1.000 cm. A final absorbance in the range between 0.4 - 0.5 is desired to calibrate in the range of the unknown solutions. You are to make up 500.0 mL of the calibration solution in a volumetric flask. Do you need to pipette 1.00, 2.00, 3.00, 4.00 or 5.00 mL of the stock solution into the 500.0 mL volumetric flask to provide a solution in this absorbance range? Show your work. (4 marks) f) Arrange the following transitions from the highest energy transition to the lowest energy transition? n -> a*, n -> n*, a - a *, n -> n* (1 mark)

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QUESTION 2 a) Briefly define the following terms: i) dipole moment ii) interferogram iii) Michelson interferometer (3 marks) b) Predict the most suitable compound, with the given the molecular formula C 7 H 6 0 2 that can fit the IR and NMR spectra below. (The peak near 80 ppm in the 13C spectrum is the solvent.)

Infrared Spectrum

B. 30

3500

3000

2500

2000

1500

1000

Wavenumber (cm-1)

13

C NMR Spectrum

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schi

T^D

rh

rh

T^D n h BG *H NMR Spectrum

sis

dr

1H (exchanges)

1H

2H 2H

_K_i.

li

dl

IT"
(8 marks)

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c) Explain the physical phenomena of the Raman effect. (5 marks)

QUESTION 3 a) Briefly define the following terms as used in nuclear magnetic resonance spectroscopy: i) coupling constant ii) chemical shift (2 marks) b) Draw a block diagram of an NMR spectrometer. Label each component completely. (4 marks) c) Predict a tentative peak assignment of 1HNMR and 13CNMR spectra for benzaldehyde . (For full credit be sure to label each signal clearly and assign the chemical shift of each peak.) (8 marks)

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PARTB

QUESTION 1 a) Describe the principles of Atomic Emission Spectrometry (AES) and of Atomic Absorption Spectrometry (AAS). Include in your discussion the mechanism of obtaining the atomic vapour and how the signals obtained in each technique is related to the amount of analyte in the samples analyzed. (8 marks) Explain why electrothermal atomizers result in greatly enhanced sensitivity compared to flame AAS. (4 marks) An analyst notes that a 1 ppm solution of sodium gives a flame AAS signal of 110, while the same solution containing 20 ppm solution of potassium gives a signal of 125. It was observed that a 20 ppm solution of potassium exhibit no blank reading. Explain the observed results. (4 marks) State and briefly describe two methods of sample introduction in an inductively coupled plasma. Which of the two methods can be used to introduce solid samples? (5 marks) Calcium in a sample solution is determined by Inductively Coupled Plasma (ICP-AES). A stock solution of calcium is prepared by dissolving 1.50 g CaCI2.2H20 in deionized water and diluting it to 1.00 L. Working standards are prepared by diluting the standard solution as shown in the table below, with the final volume of each being 100.00 mL. Standard Volume (mL) 0.00 5.00 10.00 15.00 20.00 Sample Intensity 0.0000 0.2380 0.4220 0.5999 0.8120 0.6280

b)

c)

d)

e)

i) Calculate the concentration of each working standards in the table in units of parts per million (ppm). (2 marks) ii) Determine the concentration of calcium in the original sample if the sample intensity reading in the table above was obtained by taking 5.00 mL of the original sample and diluting it to 25.00 mL solution. (5 marks)
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QUESTION 2 a) Compare and contrast the design and optical components of a single beam ultraviolet visible (UV-Vis) absorption spectrophotometer and fluorescence spectrophotometer. In your discussion include the differences observed and explain why these differences are necessary. (8 marks)

b) The relative fluorescence intensity at a wavelength of 228.8 nm of a 12.5 x 10"5 M cadmium chloride solution was measured to be 75.4. What is the concentration of a cadmium chloride solution with a measured intensity of 50.5? (3 marks) c) Rank the following compounds in order of highest to lowest quantum efficiency (OF) and explain your answers. Indicate if you think the compound does not fluoresce (OF = 0).

(0

(v) (4 marks)

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QUESTION 3 a) Briefly explain the principle used in an electron impact ion advantage and one disadvantage of this source. source and state one (4 marks) b) How could the following isomers be differentiated by mass spectrometry? CH3 CH3 _ CH2 - CH2 - CHCH3 and CH3""C OH (5 marks) CH2 _ Cri3

OH

END OF QUESTION PAPER

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