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Page 1 This question paper consists of four printed pages, each of which is identified by CMNS128001 CMNS128001 Drawing instruments and electronic calculators may be used. University of Leeds Examination for the Degree of BSc Nanotechnology (May 2011) CMNS1280: Molecular electrochemical mechanisms in bionanotechnology Time allowed: 2 hours The Examination Paper consists of 5 questions - all of which carry equal marks. Attempt three questions Do not write or draw with red ink or red pencil To obtain full marks candidates must show how answers are derived All symbols not specifically defined have their normally accepted meanings Page 2 CMNS128001 1. (a) The understanding of the mechanism of galvanic, static and electrolytic cells is fundamental to electrochemical processes which involve the interaction of electrical energy with chemical reactions. (i) Explain the fundamental difference between galvanic, static and electrolytic cells. [4 marks] (ii) In a galvanic and electrolytic cell, which reaction takes place at the cathode: reduction or oxidation? [1 mark] (b) (i) What is the lead-acid accumulator? What are the two electrodes in the charged cell of a battery and what are the two electrodes in a discharged or "flat" cell of the battery? What is the electrolyte used? [6 marks] (ii) By writing the equations for the two chemical half reactions explain how the lead-acid accumulator works. [4 marks] (iii) What is the voltage that each cell of a lead-acid accumulator generates? (iv) Name two factors which degrade a lead-acid accumulator's performance. [1 mark] [2 marks] (v) Detail the difference in operational mechanism of a lithium ion diffusion cell to a leadacid cell. [2 marks] 2. (a) Polarography is a highly elegant technique invented by Jaroslav Heyrovsky for which he received the Nobel Prize in 1959. (i) What is the unique feature of polarography which separates it from other electroanalytical techniques? [2 marks] (ii) Sketch a polarogram and label two important details of the polarographic wave on your diagram. [4marks] (b) Electrochemical or electrolytic reactions at electrodes are categorised into reversible and irreversible reactions. (i) Why does an electrochemical process appear irreversible? [2 marks] (ii) Explain with a sketch how the polarographic current-potential curve characterising an electrochemical process of reduction changes when the process becomes irreversible. [3 marks] (iii) What is the potential value in mV of the separation between the anodic and cathodic peaks of a reversible one electron cyclic voltammogram? [2 marks] Page 3 CMNS128001 (c) (i) Explain the principle behind the working of an ion selective electrode. [2 marks] (ii) A glass electrode is a specific example of an ion selective electrode. How does a glass electrode work? [2 marks] (iii) In your answer sketch a diagram of the glass electrode labelling important details in it. [3 marks] 3. How might proteins such as enzymes or antibodies be modified to improve their stability or otherwise change their properties? [12 marks] Briefly describe the biological organisms in which the new proteins might be expressed and the advantages and disadvantages of these expression systems. [8 marks] 4. (a) Describe the approaches that might be used to manufacture a biosensor electrode. [8 marks] (b) Describe the approaches that might be used to attach an enzyme or antibody to this electrode to produce a functional biosensor. [12 marks] 5. Although polarography was initially used as an analytical technique for heavy metal ions in water its sensitivity was never high and the lowest detection limit obtained was about 10-4 mol dm-3 of a heavy metal ion. Anodic stripping voltammetry (ASV) was subsequently developed as a suitable analytical technique for heavy metal ions in water. (a) (i) Describe the principle of ASV and state why it is advantageous compared to polarography? [3 marks] (ii) Sketch the potential programme used when carrying out an ASV experiment. [3 marks] (iii) Name four common toxic pollutant heavy metal ions which can be determined using ASV. [4 marks] Page 4 CMNS128001 (iv) Name two working electrode systems used in ASV and draw sketches of them with their critical operating parts. [4 marks] (b) Zinc oxide (ZnO) nanoparticles are known to release soluble Zn2+ ion. This solubility varies as a function of solution pH. The lower the solution pH, the higher the solubility of the ZnO. If a centrifugate of a ZnO dispersion is analysed for Zn using inductively coupled plasmamass spectrometry (IPC-MS), a higher value of Zn in the centifugate is obtained than when using ASV. Please explain the reason for this observation. [3 marks] (c) Explain what is meant by adsorptive (or cathodic stripping voltammetry) and explain the principles behind it. [3 marks] END OF PAPER