CHEM343 Class Test Monday 3rd September, 2012

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Instructions:

Attempt all questions. Marks are allocated to each question (total 90 marks). Please put answers into the answer books provided.

Time allowed: 90 minutes

Number of Pages: 6 _________________________________________________________

Page 1 of 6

1.

(35 marks) Answer two of the following three parts (a-c) (a) Electrochemical measurements are frequently made in a three-electrode cell comprising a working electrode, an auxiliary electrode and a reference electrode connected to a potentiostat. The electrodes are placed in an electrolyte solution containing the electroactive species. Assume that the electroactive species is R, the reduced form of a redox couple. (i) Explain how the system described above can be used to oxidise R and allow the current for the oxidation to be measured. Include in your answer a description of the function of each of the systems components (electrodes, electrolyte solution and potentiostat). Note: you do not need to describe a specific electrochemical technique or experiment. Define the term electrochemically reversible and explain why such systems are also described as being Nernstian.

(ii)

(b)

The Butler-Volmer equation is given below: (1-)nF -nF - exp Error! Bookmark not defined. i = io exp RT RT (i) (ii) State the conditions under which the Butler-Volmer equation holds. On a single diagram, sketch current-overpotential curves for the anodic, cathodic and total currents, as predicted by the Butler-Volmer equation, for the redox reaction:
O + e

Label the curves ia, ic, itotal and indicate the redox reactions occurring in each case. Indicate io on your diagram. (iii) Sketch a Tafel plot that could be obtained from the itotal vs curve in (i). o Explain, qualitatively, how k may be obtained from the Tafel plot (Note: you are not expected to derive the Tafel equations.) What is the significance of k ?
o

(iv)

Page 2 of 6

(c)

The figure below shows proof-of-concept for the electrochemical detection of glucose using the enzyme glucose oxidase (GOx) and the mediator ferrocene monocarboxylic acid (FCA). For the cyclic voltammogram labelled a, the solution contains FCA and D-glucose; for cyclic voltammogram labelled b, the solution contains FCA, D-glucose and GOx. (i) (ii) (iii) (iv) Considering only the forward scan, explain, using concentration profiles, why voltammogram a has a peaked shape. Give equations that describe the chemical reactions that occur when FCA is oxidised in the presence of GOx and D-glucose. Explain why voltammogram b reaches a much higher current than voltammogram a. Explain why nearly all commercial electrochemical glucose sensors are based on reactions with artificial mediators, rather than relying on reactions with oxygen or on direct electron transfer between glucose or GOx and an electrode.

Page 3 of 6

2.

(10 marks) Explain the statement electrochemical techniques enable the rates of electron transfer and mass transport to be widely varied, hence yielding either kinetic or mass transport information, as required. Hint: consider what determines the rates of electron transfer and mass transport, how these can be controlled in an electrochemical experiment, the information that can be obtained under electron transfer, mass transport and mixed control, and how a system might be switched between these forms of control.

3.

(a)

(12 marks) Contrast anionic with free radical polymerization with respect to reaction mechanism reaction conditions initiators used molecular weight vs conversion evolution. Illustrate your answer by using a suitable monomer for each polymerization. (4 marks) Two very important reaction steps in radical polymerization are chain propagation and termination. Identify the reason why the rate coefficient for the termination reaction, kt, is strongly dependent on the chain length of the macroradicals, whereas the propagation rate coefficient, kp, is almost chain length independent. (7 marks) The Mayo equation can be used to calculate number-average degree of polymerization, DPn. State the Mayo equation, identifying all terms. Does the Mayo equation give access to the instantaneous or cumulative degree of polymerization, and what is the difference between the two? (4 marks) An important way of controlling molecular weights in conventional radical polymerization is via the addition of transfer reagents. To what species and molecules can transfer reactions occur? (5 marks) A special type of transfer is transfer to polymer by backbiting. What monomers are prone to undergo backbiting reactions and why? Select a suitable monomer and illustrate the reaction via a reaction sequence.

(b)

(c)

(d)

(e)

Page 4 of 6

4.

Anionic polymerization can be used to prepare complex architecture polymers. The scheme below presents an anionic polymerization:

Br

Br

Br

Br OCH3

1) OH

2) s-BuLi, benzene

Li+

Li+

+ BuH OCH3 O

+ Li+

Li+

Li+

1)

2) MeOH

?
(a) (5 marks) Based on the chemical reactions given above, draw the chemical structure of the resulting polymer. (Hint: In the above synthesis, the first step is used to prepare the initiator, and the second sequence affects the polymerization.

Page 5 of 6

(b)

(2 marks) What is the role of the methanol in the second step above? (6 marks) What amount (in grams) of the lithiated precursor molecule generated in the second step would you require in order to obtain 25 g of final polystyrene polymer with a number average molecular weight of 60 000 g mol-1 at 100% of conversion of styrene? (Data: Mprecursor = 486 g mol-1. MLi = 7.0 g mol-1)

(c)

END OF PAPER

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