Jimma University, College of Natural Sciences, Department of Chemistry

Advanced electrochemistry Assignment for physical chemistry students, March 2023

 Directions: Attempt the problems carefully and solve them accordingly. Once you
complete submit the solutions in hard or soft copy before April 20, 2023.
1. What is surface tension and why it changes with potential?
2. Explain how to determine the potential of zero charges (PZC) of Hg in contact with 0.1M
NaCl. Provide specifics about the experiment and show what the data would look like
3. Name and describe the three modes of mass transport. Illustrate the concentration-distance
profile for 𝑂𝑥 in the following redox equation Ox + Red, when under non-steady state
condition and steady-state diffusion condition. What is and what factors control its
magnitude?
4. How an electrolytic reaction is influenced by electrode potential?
5. How the electrode potential is established at equilibrium?
6. For the reaction of couple Fe(III)/Fe(II) has a formal potential of +679 mV vs SHE in 1 M
H2SO4 standard rate constant is 2x10-6 cm/s and has a transfer coefficient of 0.5. The
electrode area is 1 cm2 for a solution containing 10 mM Fe(III) and 1 mM Fe(II). Calculate
the equilibrium potential vs SHE and the exchange current density. Then use the Tafel
equation to calculate current density at different voltages( 100 mV, 875 mV and 775 mV )
7. Consider the reaction of 𝑶 + 𝒏𝒆− ⇌ 𝑹 Under the conditions that 𝐶𝑅∗ =
𝑐𝑚
𝐶𝑂∗ = 1, 𝑘 0 = 10−7 , 𝛼 = 0.3, 𝑎𝑛𝑑 𝑛 = 1
𝑠
𝑖0
(a) Calculate the exchange current density, 𝐽0 = 𝑖𝑛 𝜇𝐴/𝑐𝑚2
𝐴
(b) Draw the current density-over potential curve for this reaction for currents
𝜇𝐴
up to 600 𝑎𝑛𝑜𝑑𝑖𝑐 𝑎𝑛𝑑 𝑐𝑎𝑡ℎ𝑜𝑑𝑖𝑐. 𝐼𝑔𝑛𝑜𝑟𝑒 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑒𝑓𝑓𝑒𝑐𝑡𝑠.
𝑐𝑚2
(c) Draw Tafel plots for the current ranges in (b)