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Redox Titrations
Coulometry
Voltammetry
Randles-Sevcik equation:
⁄2
ip = (2.69x105 )n3⁄2 A • D1o • υ1⁄2 • Co∗ … Randles Sevcik Eqn
Test 1
59
∆Ep = Epa − Epc = n mV
Test 2
59
|Ep − Ep⁄2 | = mV
n
Test 3
iap
=1
icp
Test 4
ip is proportional to square root of the scan rate. That is ip α √υ
Page 1 of 6
Test 5
Ep is independent of υ (the scan rate)
Haque, F., Rahman, M. S., Ahmed, E., Bakshi, P. K and Shaikh, A. A. (2013). A cyclic
voltammetric study of the redox reaction of Cu(II) in presence of ascorbic acid in different pH
media. Dhaka Univ. J. Sci., 61(2), 161-166.
Table 1: Data for the effect of scan rate on the peak current and peak potential of 1.0 mM
Cu(PBS) at pH 5.30
Page 2 of 6
Question 1 [15 marks]
(a) Apply diagnostic test 3 to the above results and conclude appropriately.
[5 marks]
(b) By means of a suitable graph, establish if the reaction studied above is reversible or not.
[10 marks]
⁄2
ip = (2.69x105 )n3⁄2 A • D1o • υ1⁄2 • Co∗ … Randles Sevcik Eqn
The following polarographic data (Table 2) was obtained for the reduction of Pb2+ to its
amalgam from solutions that were 2.00x10−3 M in Pb2+ , 0.100 M in KNO3, and that also had
the following concentrations of the anion L− . You are further told that E1⁄ is the half-wave
2
potential.
-
Concentration of L E1/2 versus SCE
3
(moles per dm ) V
0.0000 -0.405
0.0205 -0.473
0.0615 -0.504
0.1007 -0.516
0.3000 -0.544
0.5000 -0.556
Assume that the diffusion coefficients for the complex ion and the metal ion are equal, and
that all activity coefficients are unity.
(b) Explain the meaning of the following terms which appear in the Lingane equation.
(i) n [1 mark]
(ii) x [1 mark]
(iii) Kf [1 mark]
(c) Using your equation in (a) above, plot the results in Table 2. Make sure the examiner will
see the actual Table of results that you have used to make your plot.
(d) Calculate the slope of your graph (correct to 3 sig figs). [2 marks]
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(e) Use your graph to determine the value of x. [1 mark]
(g) Use your graph to determine the value of K f (correct to 3 sig figs).
[2 marks]
(h) Using the value of x from (e), write the formula of the Pb-L complex given that the ligand
carries one negative charge. [1 mark]
(a) Write the Randles-Sevcik equation. Give the meaning of each term in the equation.
[3 marks]
(b) Name four electrodes which can be used as working electrodes in Voltammetry.
[2 marks]
(c) Compare and contrast Differential Pulse Polarography (DPP) and Square Wave
Voltammetry (SWV) in terms of:
(ii) Principles of each technique. Your answer should include the following:
[4 marks]
Please make it very clear to the examiner which answer [in (c) (i) and (ii)] is for which
electroanalytical technique!
(d) Explain two advantages of Square Wave Voltammetry (SWV) over Classical Polarography
(CP).
[2 marks]
Page 4 of 6
Coulometry, Voltammetric Analysis and Striping Methods
0.0592 i
EDME = E1⁄2 − log ( ) … Polarographic halfwave Eqn
n id − i
• Polarography
• Cyclic Voltammetry
• Differential Pulse
• Normal Pulse
• Sampled DC
(a) An excess of HgNH3 Y 2− was introduced to 25.00 mℓ of borehole water from Tsolo, in the
Eastern Cape. Express the hardness of water in terms of ppm CaCO3 (correct to 1 decimal
place) if the EDTA needed for the titration was generated at a mercury cathode (Equation 1
below) in 0.08 hours by a constant current of 81.6 mA.
[10 marks]
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Question 5 [10 marks] … from the second year archive
A 0.675-g sample containing CCℓ4 , CHCℓ3 and inert organic species were dissolved in
methanol and electrolyzed at -1.0 V until the current approached zero. A coulometer
indicated the charge required to complete the reaction, as given in the first column in Table
5.1 below. The potential of the cathode was then adjusted to -1.8 V. The additional charge
given in the second column of Table 5.1 was required at this potential.
76.22 415.98
As you answer (a) and (b) below, make sure that the examiner can follow your
logic/calculations.
(a) Use the results in Table 1 to calculate (correct to 3 sig figs) the percentage of CCℓ4 in the
mixture.
[5 marks]
(b) Use the results in Table 1 to calculate (correct to 3 sig figs) the percentage of CHCℓ3 in
the mixture.
[5 marks]
Page 6 of 6